If you are not already using the quick select tool you should give it a go - it can be far more efficient than the magic wand or magnetic lasso tools.
Photoshop doesn't come with the same one-click ability as Illustrator to make the fill of shapes or objects transparent. Here's a workaround.
My favorite tool of all the pen tool allows you maximum control over drawing shapes and paths. It can be a little tricky to master at first but once you are up and running you won't look back.