What I want from DM-books, is inspiration. Although the choice of which book is the best will depend partly on the individual DM's preferences, I can say which ones I liked and which ones that didn't inspire me. Let's start with the dull and pedestrian.
The adventurer's vault was incredibly boring. Magic items are not my favorite part of 4E, and the endless wall of "1d6+Int damage, slide 1, etc." just made me fall asleep. Now, I'm not saying that these items are boring ingame, but it sure is boring to read them. Much of 4E is like that, which is why I think the DM-books are important. Adventurer's Vault 2 was slightly better in this regard, but I still didn't like it. I hope Mordenkainen's Magnificent Emporium (or whatever, can't quite remember the title, I'm thinking of the new magic item book in 2011) will improve magic items.
The three books, discounting campaign settings, that have really grabbed me, are Underdark, Demonomicon and MM3. The Underdark book has awesome fluff, and I really like how Torog sort of binds the book together thematically, without making him overshadow all the other threats and dangers. The art is very nice, I especially like the pictures on page 79 and 80, under the heading "Sunless Seas". Those fantastic landscapes are great. They make me dream of distant worlds. The opening illustration for chapter 4 is awesome. Another thing I like about the book, is the weirdness of it all. I especially liked the mushroom fortress that moved around the Underdark, forever heading to some unknown destination. It's a shame that the monsters in Underdark don't have the MM3 treatment, with the improved math and all.
I also love the Demonomicon, though I just got it and want to read more before I make up my mind. It's great how the monsters, especially the demon lords, get a lot of flavour text. The MM3 also has some nice flavour.