Still pretty sure that both of the existing answers are answering the wrong question. The author mentions right in the title that he is having trouble with PATH, not connecting to his DB or configuring rails. This is the situation I got into, and this is my solution.
After getting postgres.app running and setting PATH in my .bashrc file as directed in the postgress.app documentation - http://postgresapp.com/documentation :
PATH="/Applications/Postgres.app/Contents/MacOS/bin:$PATH"
The problem was that this path setting was not taking effect after restarting terminal.app - running which psql was returning the copy in "/usr/bin/psql", this is the copy that comes installed with Lion and Mountain Lion, not the new version installed in "/Applications/". It even says in the Postgres.app instructions "run which psql to tell that the correct version is being loaded".
Anyway - the odd thing I found was that after I ran:
source .bashrc
Then the command "which psql" would return the correct version located in /Applications/.
At this point I was stumped and had to get some extra help. The guys I tapped also thought it was quite odd too, however they quickly found out that neither the .bashrc OR the .profile files were being loaded. This is very strange, I have not seen this on any of my other macs running leopard through lion.
Now finally the solution- I am not sure this is proper, but it did permanently fix my problem. We found that their was one profile file being loaded into the terminal - the .bash_login file. In the end the solution was just to use the .bash_login to source the .bashrc file. Here is the edit to .bash_login:
source $HOME/.bashrc
And that did it.
Anyway I can't say that this is exactly the fix that diego needed / was looking for, but it is definitely the problem for me.