Yup-3 parts elbow-grease, 2 parts tears & sweat. I had a lot of data to work through, so I used that as an excuse. Not having to worry about performance, schemes, servers, users, etc., made learning a lot easier, I think.
I started by reading the tutorial in the PG docs[1]. It was _very_ well-written & accessible--def. recommend.
Later, I picked-up the book "Mastering PostgreSQL in Application Development"[2]. It was pretty solid, and seemed one of the only books aimed at developers (as opposed to DBAs).