Photoshop has much better image adjustment controls, layers, text engine etc. If you want to distort or warp a section of your art (ie tweaking the shape of the head etc.) then nothing is better than Photoshop's bezier warp tool (The one with the control handles). The only real advantage of Painter (but it's a big one) is their natural media emulation (ie watercolor, chalk, gouache , oil paint etc.) Their glow tool and blenders are fantastic too.
You should definitely check out Painter and see if you like it, but don't feel like you wont be in the cool crowd if you decide to use Photoshop Ideally you can use both - exploiting each one's strengths for different parts of the process.
I know what you mean and i agree 100%. Those tools in Photoshop are amazing. I just like the paint emulation, it looks really great. I paint once in a while and it would be cool to see the effect digitally.
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