I would distinguish between soundtracks, and "songs from the motion picture..." compilations.
For soundtracks, I would name:
Apocalypse Now (it does contain "The End" by The Doors, but most is compositions by Walter Murch featuring Mickey Hart & The Rhythm Devils, and spoken word pieces from the film by Martin Sheen)
The Godfather (I and II)
Twin Peaks: Fire Walk With Me
Destroy All Monsters (a Toho Studios Godzilla film - has an epic score)
Love & Death (Woody Allen film, all music by S. Prokofiev)
For "songs from the motion picture..." compilations, I would name:
The Harder They Come
The Big Chill
If we're going to include concert films and/or documentaries, I will add:
Stop Making Sense
The Last Waltz
The Decline Of Western Civilzation (1 and 2)
That is all.