If you've got some mathematical/crypto function, chances are you don't want that to go through a command queue to an external port, because that's too much overhead. If it's a many round crypto function like bcrypt or something, you do need to be a bit careful doing it as a NIF because of runtime. But you wouldn't want to put a sha256 through an external program and have to pass all that data to it, etc.
Something that you might actually want queueing for and is likely to have potential for memory unsafety like say transcoding with ffmpeg, would be a good fit as an external Port rather than a NIF or a linked in Port driver.
We do have IPC handles that could enable this over, say, ports, but then there's a whole other discussion on pointers vs ipc handles