GREAT ride, you'll have a great time. I'll be out there myself in a week, and I'm very excited about heading out there.
Here is a writeup I did on my last visit.
http://www.bikeforums.net/showthread...and-San-Marcos
The best time to visit and ride is early spring / late fall when there is less traffic. I have found the residents of San Marcos and New Braunfels to be very patient and friendly with cyclists. However, this time of year there are lots of tourists there for camping and floating the river, they are not as tolerant nor are they as aware of what's going on around them. As far as the ride, the best bet is to park in municipal parking in Gruene right across from Gruene Hall. From there head West to the Loop then up to River Road. River Road itself is mostly flat, but there are some short steep climbs, especially early on. After that head east to FM 2763 and then onto FM 306. On the first part of FM 306 there is a very healthy climb followed by a descent back into New Braunfels and onto Gruene Road. That should be about 28 miles with around 1500 feet of climbing or so. That is the clockwise loop. Doing the loop counter clockwise takes out the steep hill on FM 306 and isn't as much fun IMHO. I've attached a map of the simple loop I described above. There is a longer route, going from 306 to Purgatory Road, down to San Marcos, and down Hunter Road back to Gruene. That route is about 52 miles.
One thing to watch out for is River Road is very narrow. There are no shoulders on River Road, so you will have to ride in close proximity to cars, so prepare yourself. Last time I was there, I had to turn back due to repaving of the road. However I believe all that has been taken care of. This time of year, it is best to get up as early as possible to avoid weekend traffic. Once you hit FM 2763 and 306 there is a healthy shoulder, so you will be fine there. It's a great area to ride in and I think you'll have a great time. If you haven't been yet, you MUST go eat at The Gristmill restaurant before you leave.
Hope that helps, PM me if you have any more questions.