If you feel like ZBrush is a little intimidating to learn, you are not alone. ZBrush looks, feels and works differently that any other DCC app. The menus are in alphabetical order, weird! Luckily with some persistence and a few helpful tutorials, anyone can pick up ZBrush after a while. If you are looking to learn more about Zbrush’s layering workflow for texture painting, then Damon Lavenski’s tutorial might be a great place to start.
Damon is a 3D Generalist over at Psyop Studios, brought on to model, rig, simulate cloth, and render work for TV and film projects there. Damon’s tutorial is designed to help artists who would like to use Zbrush for texturing, to get more acquainted with the layering workflow. As you might have guessed, ZBrush can be similar to photoshop, but not really.
You can paint directly on models in Zbrush using PolyPaint. A simple concept, but there are a few tricks that Damon walks through that can help ease your transition to make it work best. Visit the tutorial here.