We had an applicationg running using MySql. We found MySql was not suitable for our app after we found that it didnt support some of the GIS capability that PostGIS has (note: m
While the Windows port of PostgreSQL is relatively recent, my understanding is that it performs about as well as the other versions. But it's definitely a port; almost all developers work primarily or exclusively on Unix/Linux/BSD.
You really shouldn't be running 8.2 on Windows. In my opinion, 8.3 was the first Windows release that was truly production-ready; 8.4 is better yet. 8.2 is rather out of date anyway, and you'll reap several benefits if you can manage to upgrade.
Another thing to consider is tuning. PostgreSQL requires more tuning than MySQL to achieve optimal performance. You may want to consider posting to one of the mailing lists for help with more than basic tweaking.