Sofia and Amber connecting as real friends and sisters at the end of the pilot movie.
Sofia: You have no idea how happy I was when I found out we were going to be stepsisters!
Amber: Sofia... we're sisters.
A subtle example, but in "Just One of the Princes", there's a bait-and-switch moment where Sofia thinks she's getting a majestic black pegasus to ride, but her horse actually turns out to be a small purple Pegasus with small wings named Minimus. Sofia still reacts with joy, and even when Minimus advises Sofia to switch horses (and more than once at that), Sofia adamantly insists that she can win the race with Minimus. And she's right, she does tie for first place with James.
Baileywick having tea with Sofia after she's grounded for bailing James out of trouble.
The ending of "Cedric's Apprentice": Cedric has the chance to use his invisibility potion to steal Sofia's amulet, but because she helped him prove what a good sorcerer he is, he decides against it.
Not to mention the episode's epilogue. Heck, almost all of Cedric and Sofia's interactions in that episode could count.
When Sofia first turns herself into a lizard by accident, Cedric doesn't even think for a second of using the opportunity to steal the Amulet from her, instead reassuring her that she'll be fine before casting the spell to return her to normal. Knowing that he could do it is exactly why she pulled off her Batman Gambit later.
Sofia and Clover reconciling in "Blue Ribbon Bunny."
In "The Princess Test", Amber encouraging Hildegarde to keep going in the test after Hildegarde had given up.
And Sofia passing the secret "kindness" test by agreeing to help Mrs. Higgins, and then insisting on continuing to help her even after running into obstacles (even after Mrs. Higgins tries to reassure Sofia into going back for the princess test).
In "Baileywick's Day Off", four simple words at the end after everything that happened: "Baileywick is more important."
Amber and Sofia ending up having a good time together in "Two To Tangu."
The ending of "A Little Witch". Predictable, yes, but heartwarming? Definitely.
In "Princess Butterfly", Amber is about to pull a Karma Houdini: after an episode of trying to take Sofia's amulet, Sofia finally just offers the amulet so Amber can fix her magical butterfly costume without having to admit to the fairies she cheated to win the earlier costume contest. After all, to Sofia, Amber is more important than her promise to her father never to take off the amulet. That's heartwarming enough, but then Amber turns Sofia down of her own accord, having a change of heart at the last minute. After all, it was Amber who lied and cheated to win, so it wouldn't be fair to make Sofia give up something.
The end of the two-parter "The Floating Palace" when both humans and mermaids are getting along well.
Sofia: I'm glad everyone's getting along.
Oona: Me too! It means we can be friends.
Sofia: It means we can all be friends now.
The end of "Holiday In Enchancia", with Sofia, Amber, and James giving their Wassailia presents to the peasant family who has given them shelter from a blizzard. Also when Sofia and Amber hug each other during the ending song.
After defeating Miss Nettle in "The Enchanted Feast," Sofia and Cedric share a brief but sweet hug.
Despite being a source of discomfort for Sofia, seeing Amber and James so eager to spend Mother's Day with Miranda in "Mom's the Word" is very sweet.
In "The Silent Knight," Aunt Tilly shows that she doesn't have problem with Sir Bartleby's voice, telling him she likes "one-of-a-kind things."
Cedric finally proving himself a capable sorcerer, thereby earning his perfectionist father's respect, in "Mystic Meadows."
Sofia and Hildegarde's friendship in "The Princess Stays in the Painting".
A very minor case, but in Hildegard's sad flashback, we see her big sister, who not only invited little Hildy to play with her, but showed concern when she fell down instead of laughing at her like everyone else. It's nice to think that someone as self-conscious as Hildegard might have a Cool Big Sis in her life.
Similar to "Baileywick's Day Off," we see that Sofia and the Royals fully consider Baileywick a member of the family in "Baileywhoops."
Also in that episode, Cedric makes peace with a former class rival, Greylock, and the two work together to save the assembled royals. And Greylock makes sure that Cedric gets his due credit for it, earning a round of appreciation from Roland, something Cedric clearly appreciates.
Everything concerning Sofia and Amber in "The Curse of Princess Ivy", especially Amber Taking the Bullet for Sofia.
Throughout "Winter's Gift," Sofia tries to find a special gift for Cedric. In the end, Sofia gives him a homemade wand case, and he's absolutely delighted.
So much so, that he uses a spell to summon snow for Wassalia, essentially the same type of spell he complained about as a "parlor trick" in the pilot movie, but here he does it gladly and without complaint.
Cedric coming to teach Sofia's magic class in "Substitute Cedric." Naturally, the sorcerer only agreed to it because he needed an herb from Royal Prep's greenhouse, but by the end of the episode, Cedric has had so much fun with the kids that he continues the lesson.
From the same episode, we see Cedric as a child, and he is adorable!
When Cedric learns that Sofia has been granted an invite to meet Merlin, his idol, he doesn't even express jealousy, telling her with great enthusiasm that she's been granted quite the honor. The scene only gets all the more touching when Sofia says that the invite allows her to take two guests, and since she knows how much Cedric idolizes Merlin, he was the first person she thought of.
"Dads and Daughters Day" has Sofia doubting if King Roland is her real dad, since he is her Stepfather. During a school field trip with Roland and Amber, Sofia ends up feeling increasingly like a third wheel. Luckily Roland and Amber are both adamant that Sofia is Roland's real daughter even if he wasn't there from her birth and at no point is she considered just a stepdaughter.
Sofia discovering Roland's pocket watch has two pictures in it: One of Amber and James, which she saw first, and another of her.
"Camp Wilderwood"has James and Wendell legitimately getting along.
"Elena And The Secret Of Avalor" has many including, but not limited to:
Elena being reunited with Isabel and their grandparents
Elena hugging Sofia after being freed
Sofia encouraging Elena by saying that she's not alone
The Royal Family and everyone in Avalor helping Elena overthrow Shuriki
Sofia finally revealing the secret about her amulet, and the family being cool with it.
"Lord of the Rink" has Prince Hugo's father, King Garrick, doing everything he can to spend more time with his son. After seeing Sofia and Hugo perform in an ice-dancing recital, Garrick goes up to the pair, expected to reprimand Hugo for doing something he wasn't supposed to do only to exclaim that his son has done a wonderful job. Despite having said that ice-dancing was for girls, Garrick admits that he's proud of Hugo and hugs him right in front of an audience with Hugo enjoying it instead of complaining and feeling embarrassed. The scene gets more touching when Garrick chooses to be the assistant coach for the ice-dancing class as a way to keep bonding with his son.