Hey Ben,
I have been to Big Bend "BIBE" four times and I still haven't seen all I want to see. I am partial to Indian Head because of the connection to the native americans that populated the area and also to Terlingua Abaja near Castolon.
1) Indian Head-Can be accessed from behind Big Bend Motor Inn via a walkers gate. Follow the trail around the mountain and you will see remains of were Indians lived along with some pictographs. There is a natural spring further down the trail. Also, the trail isn't that hard with little to no elevation change. Great area to explore.
2) Castolon, Terlingua Abaja, and Santa Elana Canyon-Great views along the river and Terlingua Abaja has some ruins of old adobe homes and graves.
3) Hot Springs is a neat place to see another old adobe building and some pictgraphs along the trail to the river and hot spring.
4) The Ross Maxwell Road is a great place to set up for sunset shots of the Chisos Mountains. For a split second they become a beautiful pink color if the sun light is right.
5) The Old Ore Road-Four wheeler is a must and it takes hours to drive. Lots of tinajas to photograph and explore.
6) The Basin and the Window up in the Chisos as well as the South Rim.
These are just a few suggestions and there are many more places to enjoy. I would suggest going to
U.S. National Park Service - Experience Your America and explore the information there and also at
Bend it Like Maxwell! Real Big Bend National Park Advice from Avid Benders! for more suggestions. I have added the link to my Big Bend photos for you to see some of my favorite places inside and outside the park.
Big Bend National Park