A SPOT will only work if you can see the sky. If you're in a deep canyon where there's not simultaneous line of sight to enough GPS satellites, it won't work. PLB's these days all include GPS, but GPS isn't needed in order to make the device work.
There seems to be some anecdotal evidence in real-world use that SPOTs are extremely unreliable: http://www.backpackinglight.com/cgi-bin/backpackinglight/forums/thread_display.html?forum_thread_id=25583&skip_to_post=291623#291623
A SPOT will continue signaling for longer than a PLB.
You didn't ask about price, but the yearly subscription for a SPOT is a huge rip-off. You're paying for the features such as messaging and "I'm OK," which may reassure your family but will not do much for your safety.
SPOT and PLBs are for use on land. If you were going to be, e.g., sailing across the Pacific, you'd want a different, specialized device.