If the postgresql is 7.0.2, I would highly recommend it. 6.5.3 had some issues with buggy parsing that could cause some headaches with fancy where clauses that seem to have been taken care of with 7.0.2.
As for mySQL, it's pretty good for simple table storage and recall, but if you want triggers, subselects, stored procedures et. al. it's not the right database for you.
Personally, I'd probably use gdbm for simple stuff rather than mysql, it's fast, simple, and great for single key hash table databases.
If you do use postgresql, avoid persistant connections. On smaller or poorly configured machines, you can run out of backends quickly.