I use Painter 10 for making maps (and drawing and painting in general). I don't combine it with PS or other programs, except for some stuff Painter just doesn't do (well), like manipulating selections and the brush apparently called 'Airbrush Pen Opacity Flow'. I haven't found any equivalents in Painter to that brush. I made a walkthrough quite a while ago, which I never finished, to my shame .

It's pretty exclusively a program for drawing and painting. It simply doesn't do much else, and you have to take your time to get used to the brushes and find out what they do, and what you can use them for. I only use a few brushes, especially the oil pastel, which will throw colour on your canvas or blend, depending on the pressure you use with your tablet.

I haven't yet made any mapping symbols using Painter (or ever, for that matter), but I can easily see it being used for drawing/painting that.