from <module> import * takes all names in a module (those that don't start with a _ or everything listed in <module>.__all__ and assigns those names as globals in your current module.
If two modules define the same name, that means that the last one imported this way wins; cleanup = rflib.cleanup is replaced by cleanup = Rpi.GPIO.cleanup with the second from Rpi.GPIO import * statement.
You generally want to avoid using from <module> import *. Import specific names, or just the module itself.
In this case, you can do:
from rflib import cleanup as rflib_cleanup
from Rpi.GPIO import cleanup as rpigpio_cleanup
which would bind those two functions as different names.
Or you could just import the modules:
import rflib
from Rpi import GPIO
which gives you only the rflib and GPIO names, each a reference to the module object, so now you can reference each of the cleanup functions as attributes on those modules:
rflib.cleanup()
GPIO.cleanup()
If you need to use a lot of names from either module, the latter style is preferred because that limits the number of imports you need to do, keeps your namespace clean and un-cluttered, and gives you more context whereever those names are used in your code.