If you have the time, I highly recommend Smith's
Fishing the New River Valley. It breaks down each sub area of the river and discusses techniques and tactics, fish size and species, put-ins and take-outs, and camping spots along the river (as well as other streams, both coldwater and warmwater, in the area). It is worth it's weight in gold. Granted, I bought mine several years ago and things have probably changed a lot since then, but assuming he's kept it updated with new editions, it'd be a great pick-up.
http://www.upress.virginia.edu/books/mwsmith.html
And, FWIW, my favorite stretch of that river is from Pembroke to Pearisburg. There are lots of big smallmouth and muskies in that stretch, and it is somewhat remote and receives very little pressure. Throw in some gorgeous scenery and it is hard to beat. I have also caught a couple of very large rainbow trout in that section. I assume they made their way down Big Stony and probably were going to survive very long in the river, but all I know is that they were very long and very fat when I caught them in the New.