I'm not a fan of compilation soundtracks.....they're mostly a cheap marketing ploy. Not all the time, but certainly most of the time.
Japanese videogame soundtracks are the shhit!
Ninja Gaiden (if you're into Orchestral meets electronic meets asian instruments)
Metal Gear Solid 3 (orchestral/electronic/spy music)
Jet Set Radio/Jet Set Radio Future (bit of everything....mostly funky electronic)
Space Channel 5/Space Channel 5 Pt2 (funky! Almost Austin Powers meets modern Jap funk)
Rez (trance)
Katamari Damacy (total japanese pop weirdness - can't explain this one very well)
Ridge Racer IV, V & PSP Soundtracks (techno, but with a twist mostly)
If you're looking for something a bit different (god forbid!), then check those masterpieces out.
As for movie soundtracks, there are too many (original soundtracks) to mention.....I'm a big fan of the Matrix soundtrack(s) ....the Don Davis stuff that is....some of the orchestral/electronic stuff he did is amazing....in particular the scene where Neo, Morpheus, Trinity and Seraph go up the elevator and into the battle just before they confront the Merovingian in Reloaded, and then the motorbike/freeway scene later on.....it's awesome stuff!
The Gladiator soundtrack is good. Typical Hans Zimmer over-the-top Hollywood style score, but regardless, some of it is just awesome. I've got the "More Music From Gladiator" soundtrack as well....there's a demo version included of "The Gladiator Waltz" (the track that plays during the opening battle) that he did on computer using samples only....no live orchestra at all...... and it completely opened my mind towards what could be done with such tools. You wouldn't know it wasn't an orchestra....my jaw dropped the first time I listened to it. I actually prefer it over the orchestra/movie version.
The Amelie soundtrack is beautiful. (composed by Yann Tierson) And although it's probably insulting to the composer to suggest this, it's fantastic "clean the house" music!

Just beautiful instruments playing beautiful melodies.
There's so many more of course....maybe I'll post them as I remember them...lots of old classic that I just can't think of right now.
Compilation soundtracks are just so boring in my opinion. Sometimes they are perfect (Pulp Fiction etc....in fact, all of Tarantino's soundtracks are great examples of getting it right), but too often they are just used as a marketing ploy, and a way to make people spend a little bit more money.