That being said, you cannot expect them to be extremely effective with said guns. They may be, but it is not a given. After all, the introduction of weapons to Africa mainly allowed African kingdoms to capture more slaves to sell to European and or Islamic buyers.
But they were highly effective with guns, and their biggest obstacle was a supply of guns, tools for repairing guns, and powder for the guns. All of which Europeans would be much more eagerly helping them TTL. And I'm describing North Americans OTL. More organised states like the Inca or Mesoamericans (who might recruit European mercenary commanders to assist them) can master European firearms and modern tactics as well as anyone can--of course, tactics change in the New World based on geography. And as I suggested, a Native American slave trade would emerge and be sustained more than OTL's Native American slave trade. I think the experience of Africa is relevant to TTL's New World to some degree or another.