Maybe the daemon is started, and when you click in the app is launched the configuring client. I don't know, I've never used Firestarter. You can check it in a very simple way. Open a terminal and write:
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sudo /etc/init.d/firestarter start
Perhaps is not 'firestarter', try 'firestarterd' or something. Just dig around.
If it tells you that is already started then the daemon starts at boot time. If it shows you that is not started nor exists, then you have to start it manually. If you want the app to auto-start add it to Menu > Sessions > Startup Programs; there click add and enter firestarter or the command used to launch. And you're done.