Heh, I work really slow too. Not only when I paint but also with vectors.
Photoshop probably isn't the ideal choice for vectors but I'm too lazy to start learning illustrator. The most important vector tools in photoshop is the Pen tool which you can use to make the vector paths with splines. There's also shapes such as circles, rectangles and all that kind of stuff.
The most of my vector images were made by drawing the needed shapes with the Pen tool and then using those paths as masks for layers (solids and gradients) which I blend together. It's always a bit of a puzzle to arrange the layers to make it look good but I find that it's a part of the fun too.