drak: i'm pretty new to it myself, so take this fwiw, and you probably don't want to hear this but: the best way to learn is to just do it.
the vector tools in photoshop are pretty good, but if you want to go all the way you should try illustrator or inkscape...but just draw a lot as there's not much to it except familiarizing yourself with dragging handles. a good trick is to find a picture of what you want to draw and trace it with the pen tool.
here's a decent-looking tutorial (i just skimmed through it though).
also, i should mention, i don't think they'll work just yet. but perhaps in a future version (maybe over the weekend? but it's not my project and i'm not going to put words in anyone's mouth.)