Anyhow, start the app, open a psql shell with /Applications/Postgres.app/Contents/MacOS/bin/psql in a terminal window, and you get a session. Since (I think) the app is intended only for development use, I'm not sure if they intend for you to change those defaults. That's not to say that you shouldn't but just that the app is meant to be (nearly) zero conf. (The documentation suggests adding Applications/Postgres.app/Contents/MacOS/bin to $PATH, which is probably a good idea if you will use the command line tools often.)