Working with VRS is definitely one of the hardest things you can do in FFXI modding, partly because the program was translated to broken English, and also because of little troubles like being unable to Undo at certain points. Also, it's a program designed for creating models and reworking animations, which you're not asking about.
If all you want to do is recolor hair, you'll only need ChangeTex, Photoshop, and the Photoshop .dds plugin. ChangeTex and the plugin are available here:
http://ffxidats.caarrie.com/index.php?action=downloads;sa=view;down=1340
You're on your own for Photoshop though. When you have them all, just do the following:
1) Open the .dat in ChangeTex
2) Extract the texture as a .dds
3) Open the texture .dds file in Photoshop
4) Do your coloring thing
5) Save as the same format (.dds)
6) Import the new texture .dds in ChangeTex
7) Slap that dude into the proper folder to overwrite the old face model