I'll strongly second the Cook's Illustrated recommendation. If you want to know the reasons behind the recipes, there's no better place to start. I've used things I've learned from their articles many, many times to help with
other recipes.
And here's some books that spend at least as much time talking about how to cook as they do giving lists of ingredients.
_The Zuni Cafe Cookbook_ by Judy Rodgers
_Cooking by Hand_ by Paul Bertolli
The French Laundry book by Thomas Keller is worth a read.
If you're into charcuterie, someone else mentioned Michael Ruhlman; his book _Charcuterie_ with chef Bryan Polcyn is excellent. _The River Cottage Meat Cookbook_ is also good.
If you want to go deep into ingredients, _The Elements of Taste_ by Gray Kunz and Peter Kaminsky (and _The Flavor Bible_ by Karen Page and Andrew Dornenberg (I haven't personally read that one all the way through, though)).
And you can always just pick up a culinary school textbook.