Have you tried using the old controller again and see if that made any difference?
Have you tried hitting the off button first then hit defrost?
Normally I would say it may be a blend door actuator problem, but am confused as why with ign on without the car started, would you then only have defrost air...IDK.
I believe there is a way with a TechII scanner to do a diagnostic on system.
Hopefully others will chime soon as well.