American Beauty and Gladiator are two of my favorites. I also like the Crocodile Dundee soundtrack (not the pop-type songs, but the allegedly Australian-flavoured tunes).
Silverado has a good soundtrack, and I do own it, but I never listen to it; I only like it as part of the movie, not by itself.
Disney’s animated features generally have great soundtracks, for bounciness and cuteness, but again they fit best for the movie and not necessarily for listening by themselves.