Gator,
I just moved from there about a year ago.
Culebra:
I don't think you will be able to spearfish from any recreational dive boats. I'm not sure where you are from but in most parts of the world recreational dive boats do most of their diving in reserves where marine life is pretty abundant. Not to mention that it is down right uncouth to shoot fish in front of tourists who are trying take pictures and enjoy their once in a lifetime experience of scuba diving. If you still want to spearfish then you'll have to learn where the reserves are located in order to stay out of them. Second, you'll have to find a boat or someone to take you out. I recommend staying at Ville Boheme on Culebra. If you can't stay there then go there anyway because he has a boat that he will rent to you. Fish and wildlife has an office on Culebra where you can get all of the information you want. Bring a local or make sure you speak spanish so you'll make out better. There is a guy named Rolo who is very nice. Also a lady named Teresa. Ask them for info. If you speak to Teresa tell her Michael Solis from EOD said hi. If you can't work out the logistics then you'll have to settle for snorkeling which can be done from just about anywhere on the island.
Puerto Rico:
I don't think there are any beach dives in the Rio Grande area. There aren't many beach dives anywhere in
PR really. I did most of my diving/spearfishing/lobster hunting around the island of Vieques with a boat. The other option which I recommend if you are a deep diving freediver is to go to the other side of the island to La Parguera. Contact Angel at La Parguera divers and tell him I said hi. This is for freediving only. The black wall is great and depths range from 75-110+.
Try to work out the logists of your trip before you leave so you won't have to do it there. If you have any other questions just let me know.
Take care and have fun!!!