My learning process usually works like this:

1) Learn the syntax/guts of a tool by going through a book, tutorial and trying trivial examples.

2) Work until I run into a problem. (How do I make merb-auth work with a flash uploader?)

3) Find examples/read a book/look at API docs until I figure it out. (Ohhh, you write a Rake middleware to handle it!)

4) Goto 2.

So reading materials are important, but I usually use them to solve real problems. There's no part of this process that doesn't involve writing code.