i think the biggest problem to face first is the vector app you will be using.

there's a "crap-tonne" of great tuts out there for learning vector illustration but most assume you will be using Adobe Illustrator. Since you stated you are using CS2 it's safe to assume you certainly don't want to drop $600 a year for Adobe Creative Cloud Suite (which gives you all the Adobe Apps you could ever want - as long as your subscription is active...) so you need to look at the alternatives. Daffy34 already mentioned INKSCAPE (really good app) there are also "web-based" apps.

But to get back to your original question, take a look at:

how-to-use-photoshops-pen-tool  (she takes you through using Photoshop's pen tool which is critical to creating vector art in CS2)
she has another on called vector-art-with-photoshop that uses a photo as a template...

also: photoshopcafe.com's pen tutorial (at the end they had a link to a cool game that helped master your pen tool skills)

hope these help as a "starting-point" while you figure what vector app you want to use.

retrocity :)