I had this a couple of times. That's right, the instance is stuck, and you cannot open a new instance.
Simply kill the faulty Firefox session. On a Microsoft windows system, press alt-ctrl-del, choose "task manger", then "processes", you choose "firefox.exe" and you click "stop this process".
On a Linux system, in a command line windows you type "ps -aef |grep -i firefox", you read the process number (the leftmost number, let's suppose it's "1234") and you type "kill -9 1234" (replacing 1234 with the real process number).
After you killed the stuck firefox process, you will be able to start a new firefox session.
After repairing this, you should consider understanding why this occurs. On my own computers, this occurs with some precise sites trying to do some operations forbidden by my OS, surfing on these sites auto-kill IE6 sessions, firefox survives but sometimes freezes.
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