Best place to start is at
http://www.teambg.com. Read their
tutorials, check out their
downloads for the Infinity Engine Explorer Pro (IEEP).
As TeamBG suggests, modifying item files for items already present in the game is a good idea. You can find some of these .itm files in the Override folder in your BG2 directory, but if you can't find what you're looking for, you're going to need a .bif extractor to get the item files. (Just about everything I've referenced mentioned the wonderful Biffstripper tool, and I can't find it anywhere!

Does anyone know where this file is?)
A word of warning: if you didn't understand anything in the above paragraph, you're going to have a tough time itemmaking. It took me several posts at TeamBG to even be able to say that, let alone understand it.