I have a lot, (anything by Hans Zimmer, Danny Elfman or the unsurpassed John Williams) so I'm gonna list a couple themes that I haven't known my while life, or that were surprisingly good.

Sky fall; never thought much of adele until this point (I don't really follow contemporary music) but this song was fantastic.

The new superman music; I love John Williams to death, and this doesn't surpass his composition, but it's very sweeping, very rousing and has me more exited for this movie than I probably should be.

Inception; I know we all like to make fun of the, BWAAAAAAAA, BWAAAAAAAA BWAAAAAAAA. But the score for this movie was brilliant.

Cloud Atlas; the movie had some issues, though I did enjoy it altogether, but the actual Cloud Atlas song they composed was beautiful.

Howard Shore's Lord of the Rings score was so good that I want an option that allows me to watch the movies with just the music for sound.

There are a few songs from The Mission that get me. Specifically Gabriel's Oboe.

Randy Edelman's score for Gettysburg is too often overlooked.

The soundtrack to The Incredibles is my favorite soundtrack album- evar.

Some of the music from The Matrix Reloaded is really good (and some of it is crap).

There are also a few select songs that I have picked up and listen to frequently:
"Jack Sparrow" from Dead Man's Chest
"I am the Doctor" and "A Noble Girl About Town" from Doctor Who
"Jake Lonergan" from Cowboys and Aliens
"Battle Without Honor or Humanity" aka "The song from Kill Bill" (It's from the album "Electric Samurai" by Tomoyasu Hotei. The whole album rocks.)

Michael Nyman's score for Prospero's Books.

Patrick Doyle's score for Henry V.

Have to agree with the LotR music, and with the OP's appreciation of Zimmer, and Williams, but not with the particular works in Skyfall or Inception.

Magmoo mentioned the music, but not the composer of the Mission: Ennio Morricone. He's most known for that and the Good, Bad & Ugly, but did other fantastic work on The Professional and Once upon a time in America. He's scored another zillion movies, and I haven't seen most or noticed the music in many of them, but his works appear to me to cover a broader range than, say, Williams', where I frequently seem to hear familiar themes and arrangements.

Some other gems are Zimmer's lesser known Black Rain, Poledouris' Conan, Edelman/Jones' Last of the Mohicans, and Doldinger's Das Boot.

I also kind of like the NFL theme.

Christopher Franke (of Tangerine Dream) did the soundtracks for Babylon 5. I've got a playlist of all the B5 music that I'll sometimes play for hours on end when I need background/productivity music.
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TAZ

I have the first two already. My point is that the score conveys a lot of the emotion and energy of the story that it would be great to watch the film that way.

I have a few of those albums. I used to listen to that a lot.

I've found the stuff from Two Steps From Hell to be very enjoyable. A friend of mine even plays it for his students before tests to get them pumped. I just wish the tracks were longer or looped better.