I could do, but I wont. Here is why...
The first version of PlayerPal was actually a Windows Service. This meant it would start up, even when you were not logged in (this is cool if you have PlayerPal on a music server). However, I decided to change it from a service for the following reasons:
1. To access your WMP media library, the service had to be installed under your user account. This meant, you had to tell the PlayerPal installer what your password was, when the service was installed. This freaked a lot of people out, and slowed PlayerPal adoption. Also, it just plain confused the less technical PlayerPal users (of which there are a few!).
2. iTunes does not play well when being controlled from a service. It does things like startup, but not show a GUI. This is confusing for users, as when they tried to start iTunes, nothing would happen. Thus, when I added iTunes support, another nail was put in the service coffin :(
So, what can you do to make PlayerPal auto start after a reboot?
You can set your XP box to auto-logon. After logon PlayerPal will start up. No hands! See this Microsoft page Auto Logon to Windows XP.