Here is how to change a user's or order's email address:

1.  View the order, and click on the Customer Number
    

 

2.  Edit the user account, and update the email address
    

 

3.  Go back to the order and click its Edit tab -- use the Magnifying Glass icon to for the user by username:
    

 

4.  Select the correct user
    

 

5.  The order email address will be updated automatically