Last October, we used 64 between Chama and Taos. It is a pretty drive through a lot of National Forest, but there's not a lot of development, so don't count on any gas stations.
The High Road is scenic and quite interesting, especially the old churches to photograph - if you are short on time, focus on Chimayo. Near the church, El Potrero Trading Post sells carved religious items and inexpensive baggies of ground red or green chile powder. I've been using it all winter. The Ortega Weaving shop nearby has beautiful things, some small and quite reasonable. Their traditional wooden looms are in the same building as the shop.
I believe the High Road passes the Rancho de Taos plaza and San Francisco de Asis mission church on the way into town. But if you go the other route, it's not a big deal to drive a few minutes to see the church. Taos is fairly small in size.
You can get great photos of the church from all sides and it's fun to compare your own pictures to the work of Ansel Adams and Georgia O'Keeffe.
I love New Mexico and was glad we spent two weeks seeing the northern part of the state. Will certainly return for a third visit, maybe for the Hatch Chile Festival next time.
