Anyway, I finally got to play around with it a bit and got some basic colors down for my Suicidal Furby gun. I was going to try and texture this exclusively in Painter, but I decided that would be counter-productive and will use Photoshop as well. I'll actually use Photoshop more for adding image-type textures (logos, text, ect...). Until I learn Painter more, I feel like this will be better workflow.
Here are two screenshots of where I am. Just the basic diffuse materials on there right now. I'm liking the way the scope is coming out. I'll take that into photoshop to add a glass texture for the ends of the scope. I also like their shinny plastic preset. I used that for my "easy" button. I'll also take that into Photoshop and throw the text on top of there. I haven't fully decided on what I'll do with the ammo chamber (silver area in the back). Probably take that into photoshop to color in the furby balls. I also want to make it look "down and dirty" so I'll try to do that in Painter. They have some cool physics brushes that I can try, but I may also just add some detail in photoshop as well. I'm also still deciding on some colors for the pieces of themselves. I want to change the brackets to a different color, so I'll play with that. The handle will also be a rubber, but I have to decide if I want the full bracket piece to be rubber or just the handle.
Overall, I am starting to get a grasp on the program a bit. As more information is released on how to do basic things, I feel like I'll be able to produce more things in a decent amount of time.