I would suggest rather than monitoring the USB port you would look to monitor the print queue activity. I would imagine a scripting language would be able to do this pretty easily.
Be careful with this, some printers will "lie". We have something along the lines of twenty different printers from nearly every manufacturer at my work and they all have their "personalities". Some of the quirkiest I've ever seen. The queue on some behave correctly so you always know when they're available, others will flush the queue as soon as the print job starts (even if it's a 100 pages).
One of my damn scripts at work broke because a new printer we bought always reports a paper jam even though there's no paper jam at all. Took me weeks to figure out why the script would only work for some people.

If you have control over the software, why not alternate between printer 1 and 2 during prints? If you send the job to printer 1, the light up #1. if you send the job to #2 light up #2.