Grosse Pointe Blank has two very good "Music from the film" CDs. For OSTs, though, Fight Club, American Beauty and The Thirteenth Floor all seemed to truly capture the feeling of the films, in an abbreviated / expanded (depending on your perspective) view of the films' soundtracks.
I'm going for Tron: Legacy by Daft Punk...but i also want to say Walter Carlos' Clockwork Orange ( who wrote the original Tron music after a sex change as Wendy!!) and The Good, The Bad and The Ugly but........