Shellac is often called the universal finish because it can be used on top of or under most other finishes. It certainly can be applied over polyurethane. However, the flexibility of these two finishes is different, so there could be problems in the long term if there is movement caused by sun heating, hull flexing, etc. (both of which are to be expected during use). In any case, as MGC has indicated, polyurethane is a poor finish for wooden boats. It would be best to do whatever possible to get down to bare wood before refinishing, and you seem to be doing a good job at that.
I've been watching your posts from the beginning and given that you're so interested in doing well with this canoe, why not do a full restoration? It was a freebie and there's no family connection for you but even so, you seem to care about and respect this canoe. You might find it great fun to take it down to the bare hull and bring it back to original condition with proper materials. In the end you'll have a canoe that is in much better condition for use, and you'll have the satisfaction of knowing you did it.