I'm an artist by trade and been using Photoshop since about 95 and there's still things I don't know about it, so don't feel bad. It's a great program though and I think it's well worth the cost when you get down into it beyond the basic doodling everyone does initially. I'm a bit of a perfectionist as well so I use vectors layers and shapes. You can do a lot with those and they leave you a lot of options. I tend to work with lots of layers as well. I make each area of the texture map a separate layer and have them all neatly grouped for ease of editing. For doing the scheme in that picture, vectors would work just fine. Just make a vector rectangle of whatever color and then you can use the pen tool to edit the point of that box into whatever shape you want. After that, you can duplicate that layer to then move and edit the next stripe. The cool thing about the vector layers is you can change colors instantly with no hassle. If you want to look me up on MSN messenger sometime I can talk you through a few things to get you on the right track. I've even got a few of the planes for G2 setup into nice template type files separated into layers for a quick starting point. I can show how I make a scheme and maybe that will get you going. I think so far I've gotten the PT-40, Cap 232 and Ultimate Biplane broken into templates, with the P-51 and Giles 202 started and waiting on another rainy day. PM me if you are interested in any Photoshop help or would like one of those templates to see how I work. Good luck.

Here's a screenie of a biplane I did using nothing but vector layers and layer effects on it.