Wht that big pic I think the lines are strange blurry. If you are confused whit the brushes and drawing tools you better sketch whit a drawing program.
I find this a good program for sketching [gives a good feel on the pen and nice lines],
and then gimp to color and finish things [if u dont have a fully licence version of PS that is]:
http://www.smoothdraw.com/
*and its free as gimp!