But then think about what the routing tables would look like, how would an IPv4-only host find an IPv6 host not in pool 0? You'd be reinventing NAT, but in a less-structured context than how NAT works today. There's more issues to it too.

If it was really that simple they would have done exactly that. "Just adding more bits to IPv4" just isn't possible to do backwards-compatibly. IPv6 is the closest you can get to that while also dealing with the complexity that arises with longer addresses.