I found a couple of good tutorials on how to use the Pen tool in Photoshop (a tool I didn't like using at all and now love).
First is how to use the tool:
http://www.thegoldenmean.com/technique/pen1.html
Now, how to use the contours to "ink" your work:
http://www.deviantart.com/view/23129897/
I found both of these tutorials helpful in leanring how to use a tool I used to both hate and fear.