First, check your current config (example output in homebrew.mxcl.postgresql.plist.xml
lower down in this gist):
cat ~/Library/LaunchAgents/homebrew.mxcl.postgresql.plist
Most importantly, note the -D /usr/local/var/postgres
argument.
Second, shut down your current PostgreSQL.
launchctl unload ~/Library/LaunchAgents/homebrew.mxcl.postgresql.plist