Hi Ed,
There are massive benefits in moving to PostgreSQL. The problem for most MySQL users is because MySQL is so painfully limited, they simply don't know what they are missing out on!
For example: foreign keys, triggers, subselects, views, rules, stored procedures, custom datatypes, operators, partial indices, functional indices, etc.
Postgres also has much better transaction support, it has a write-ahead log - so you never lose data during a power off.
Coming from MySQL, it will take you a little while to come to grips with it. It also does not hold your hand! You will need to do your own indexing and you will almost certainly need to do some server tuning for best performance. BUT IT'S WORTH IT!!!
I used to use MySQL and now I cannot emphasise enough how much better Postgres is.
Hopefully on Monday, version 7.2 of Postgres will be released - I suggest using that version over all others.
Chris