[volkadav]

The postgresql.org docs are a great starting point: http://www.postgresql.org/docs/9.1/static/ for example. (They also serve as a good reference when you're forgetting some finer point of syntax or admin later... the manual's nicely "phased" in terms of introductory and reference content.)

I'm lucky enough to work at a company that tends to use Pg as our default RDBMS; speaking strictly as a dev it's a heck of a lot more ergonomic and sophisticated than some of the things I've dealt with.