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A Video Game / Anime about Idol Singers would quite obviously provide plenty of examples of awesome music, but a few of them deserve special mention for their added effect during the scene/event they played out.
Nemuri Hime - Sung by Chihaya a cappella at first, making the entrance of the orchestra all the more powerful in Ep 21. Another Awesome Moment because her passion for singing saves the day despite Kuroi's rigging of the background music, and it lets Jupiter realise what he's doing and leave for good.
Chihaya's original song from the first game, Aoi Tori. It is a beautifully melancholic piece that practically defines Chihaya's feelings. It returns as an arrange for Episode 4's ending, complete with a new recording and a beautiful a cappella performance in the episode itself.
Marionette no Kokoro - Sung by Miki in Episode 13. Doubles as a Determinator moment for her, since she was already tired from singing/dancing her previous song.
Jibun Rest@rt - Sung by 765PRO ALLSTARS (without Iori, Ami and Asuza). It's a defining moment in the series, where the idols that aren't Ryuuguu Komachi step up and prove to the world that they're just as talented and that they can stand on their own.
ALRIGHT* - One of Yukiho's image songs, which she sings in episode 3 of the anime as a way of overcoming her own weakness.
Little Match Girl - Shows how Yukiho has become confident in herself, enough to take the lead in the center of the stage with no problems. The M@STER version is even more glorious.
The last episode's performance of a mashup of the two openings, READY!!&CHANGE!!!!, in its fully animated glory. All the girls manage to hold this concert together even with their incredibly busy schedules.
ALIVE, the personal song of DS idol Hidaka Ai, a massive genki girl trying to make it as an Idol by her own merits, instead of just riding the coattails of her famous mother (as many producers have advised). Ai auditions and always gives her all, but gets rejected and fails more often than not; keeping up the cheerful persona to others, but secretly crying about it alone at a park at night. Knowing this, the song becomes that much more of a Tearjerker and serves as an inspiring theme for perseverance in general.
961 Jupiter's Alice or Guilty is fairly awesome in itself, rivalling 961 Project Fairy's Overmaster in coolness.
Tonari ni... is incredibly emotional, and the heartbreaking lyrics strongly imply that the singer is left behind by a person who passed away. The "movie" in the anime shows it as such, with Azusa whispering "I've decided to marry." at the hill mentoned in the song as she decides to move on. It's something you normally wouldn't expect from an idol series.
relations is one of the series' earliest rock-type songs.
Chihaya's Me ga Au Toki manages to be fast paced and emotional at the same time.
Makoto's image song Meisou Mind, which is incredibly cool.