The days of 'Zbrush can only be used for organic modelling' are over. There are plenty of tools inside ZBrush that can be used for non organic models.
Regarding texturing, it's always best to Unwrap a model yourself, but
UVMaster does a pretty damn good job at Unwrapping something almost automatically.
For 3d painting, turn of Zadd/zsubtract in the toolbar, make sure RGB is turned on and then turn colorize on in the tools>polypaint tab. Now you can just paint on the model just like normal. Zapplink is also fantastic as it exports a render of your model out into Photoshop so you can use all the features there for direct painting onto your model. I used some custom skin Alphas on my model
here which was all created in Zbrush's polypaint and then some final tweaking with ZappLink in photoshop.
Think of the Alphas as a mask for whatever you are painting onto your model, be it geometry, texture or even a simple colour. The one thing you have to remember about texturing
anything is;
as long as you can paint it, you can texture it.