Season 1: Sokka (the Cynic), Aang (the Optimist), Katara (the Realist) and Zuko or Momo/Appa (the Apathetic).
Season 2: Toph (the Cynic), Aang (the Optimist), Katara (the Realist), and Sokka (the Apathetic, or a milder Realist). Alternately, for the dark version which fits it even better: Zuko (the Cynic), Ty Lee (the Optimist), Azula (the Realist), and Mai (the Apathetic).
Season 3: Aang (the Optimist), Katara (the Realist), Sokka (the Cynic), Toph (the Apathetic), Suki (another Apathetic), and Zuko (another Cynic).
The Four Nations as a whole fit. The Fire Nation is The Cynic (due to thinking less of everyone else), the Earth Kingdom is the Optimist and the Realist (they're the main obstacle for the Fire Nation, but they also think hiding behind a wall will protect them from anything the Fire Nation throws at them), the Air Nomads were The Apathetic (they were the most detached from the world), and the Northern Water Tribe is The Conflicted (they want to help out, but they don't have the resources and are too isolated to do much).
The Belchers from Bob's Burgers: Linda is the Optimist, Louise is the Cynic, Bob is the Realist, Gene is Apathetic, and Tina is Conflicted.
Codename: Kids Next Door: Numbuh One - Nigel Uno (The Conflicted, shifting constantly from optimistic (almost dangerously so) to cynical depending on the circumstances), Numbuh Two - Hoagie P. Gilligan Jr. (the Optimist), Numbuh Three - Kuki Sanban (the Apathetic), Numbuh Four - Wallabee Beetles (the Cynic), and Numbuh Five - Abigail Lincoln (the Realist).
DuckTales: Scrooge (the Realist), Huey (the Optimist), Dewey (the Cynic) and Louie (the Apathetic).
Extreme Ghostbusters: Roland (the Optimist), Garrett (the Realist), Kylie (the Apathethic) and Eduardo (the Cynic).
Gargoyles: Demona (the Cynic), Goliath (the Optimist), Eliza Maza (the Realist), and Xanatos (the Apathetic).
The Mystery Shack crew from Gravity Falls: Mabel is the Optimist, Grunkle Stan is the Cynic, Dipper is the Realist, Wendy is Apathetic and Soos is Conflicted.
Later, Ford joins as a further Apathetic team member, in the "enigmatic, different/removed background/priorities" sense rather than the "uninvested."
Also, while Wendy isn't very interested/involved at work, she when coming along to the kids' adventures tends to fall into the Cynic role, occasionally contrasting Mabel's sugary, diplomatic approaches with her more pragmatic, "grownup" mentality.
The Cynic: Twilight Sparkle (Formerly), and Rainbow Dash
The Optimist: Twilight Sparkle, and Pinkie Pie
The Apathetic: Fluttershy
The Realist: Applejack, and Rarity
Twilight Sparkle can also fit as The Realist, depending on the episode, while Rarity (and sometimes Pinkie Pie) tend to show shades of The Conflicted from time to time.
The Powerpuff Girls: Blossom (the Realist), Bubbles (the Optimist), Buttercup (the Cynic), Professor Utonium (the Apathetic)
Rex The Runt: Rex (the Realist), Wendy (the Cynic), Bad Bob (the Optimist), Vince (Apathetic).
Rugrats: Tommy (the Optimist), Chuckie (the Realist), Phil and Lil (Apathetic), and Angelica (the Cynic).
Scooby-Doo! Mystery Incorporated: Fred (the Optimist), Velma (the Realist), Daphne (the Apathetic), and Shaggy (the Conflicted). The role of the Cynic is filled by various secondary character. Most notably Sheriff Stone. Interesting to note is that while they fit this pattern both philosophically and functionally Fred, Velma and Daphne have personalities more closely associated with Apathetic, Cynic and Optimist respectively.
Sidekick has the four main characters: Eric (Realist), Trevor (Apathetic), Vana (Cynic) and Kitty (Optimist).
The Simpsons: Homer and Bart (the Cynics), Marge (the Optimist), Lisa (the Realist), and Maggie (the Apathetic).
Sonic Boom: Sonic (the Apathetic), Tails (the Optimist), Knuckles (the Conflicted), Amy (the Realist) and Sticks (the Cynic).
South Park: Stan (the Realist), Kyle (the Conflicted), Cartman (the Cynic), Kenny (the Apathetic), and Butters (the Optimist).
Steven Universe: Pearl (the Cynic), Garnet (the Realist), Amethyst (the Apathetic), Rose Quartz and Steven (both the Optimist).
Teenage Mutant Ninja Turtles: Leonardo is disciplined, balanced and the group leader (Optimist, yet the Realist); Donatello is intelligent, has special skills and always busy (Realist, yet the Apathetic); Raphael is hostile, skeptical and rude (the Cynic); Michaelangelo is foolish, determined and optimistic - (Apathetic).
From VeggieTales: Bob the Tomato (the Realist), Larry the Cucumber (the Optimist), Archibald Asparagus (the Cynic), and Jimmy and Jerry Gourd (both the Apathetic).
W.I.T.C.H.: The five protagonists - Will (Realist), Irma (Apathetic), Taranee (Conflicted), Cornelia (Cynic), Hay Lin (Optimist). However, Will and Cornelia frequently swap roles depending on the situation. Also the supporting characters, Caleb (Cynic - though with strong traits of Optimist), Matt (Realist), Blunk (Apathetic), Elyon (Conflicted - then later the Realist), Aldarn (Optimist).
Xiaolin Showdown: Omi (conflicted), Raimundo (cynic), Clay (realist), Kimiko (optimist) and Dojo (apathetic).
Young Justice: At the beginning when there were only 4 members, it was Speedy/Red Arrow (the Cynic), Kid Flash (the Optimist), Aqualad (the Realist), and Robin (Apathetic). Later, when Speedy/Red Arrow left and Superboy joined them, he replaced Speedy as the Cynic and Miss Martian came in as the Conflicted.
Robin is sort of an odd duck in that he fits the apathetic definition most of the time, but this is at least partly because he doesn't like to slow down long enough to actually consult with his team members much less debate philosophy. Whenever he actually does slow down to talk strategy with the rest of the team, it's usually because the situation has gotten so bad that Robin has taken over as de-facto commander — at which point he doesn't debate; he just gives orders which the others meekly follow.