If you want to still be able to add gem 'pg' to your gemfile and use bundle install, and you know PostgreSQL and libpq-dev are installed (which I believe both should be since OS X ships with PostgreSQL) you need only tell your $PATH where to find pg_config. Try this:
$ ln -s /Library/PostgreSQL/9.1/bin/pg_config /usr/local/bin/pg_config
Make sure to replace 9.1 with whatever PostgreSQL version you have installed. And make sure wherever you're creating the link is in your $PATH. Once that's done, run bundle install to install the pg gem.