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Am I missing a state somewhere to catch instances where a user hits copy

Review your workflow logs.  Essentially the new record created should restart the entire workflow from the beginning.  So it is probably transitioning right to the approved state or something, which is locking it.  Unless you have a Lock Record action in your initial state which seems odd

In your intiate state you may need to put Set Field Value actions to set all your approval fields back to the beginning, so copied approved PO's don't start out as Approved