Shimano XT V brakes are pretty much one of the better V's out there. Avid makes some good ones as well though. The XTs are pretty light and last. You can find deals on brakes and levers on the net for cheap, especially this time of year ($100 or way under sometimes). If you ride XC in dry conditions most/all of the time V brakes are just fine (especially with ceramic coated rims).
Avid mechanicals get rave reviews (never tried them) but most dig them ($90 or under per wheel). Lots of people rave on Hayes, but I had them and never really loved them as much as I expected to based on many others views. I now ride Shimano XTs (8" rotor front/6" rear). Retail is like $190 per wheel, but you can find A LOT better deals if you spend 10 minutes on line. I paid $245 with shipping for the 2003 models when I bought them earlier this year. I read some good things about the Hope mini system for XC riders.
For me it was easy to choose brakes. When I lived in Colorado I had the XT V's with ceramic coated rims and they worked great even for the FR junk we did, but it was dry as hell in weastern CO. When I moved to Oregon it was obvious they were not going to cut it up here where the locals have webbed feet (I am starting to get some webbing myself now, cool). Tryed the Hayes for a while, but like I said I just never felt they were all that great (better in wet than the V's though, but not the dry).
It gets pricey since you have to get new hubs and spokes and all. Have fun shopping and ride well.
K.