same problem here, new order email cannot change what ever I do.
I am not trying to send emails to the client, but to a different, fixed address.
Background: I installed woocommerce as an admin with username1/email_address1 and accepted the default settings. It set the recipient email addresses for new, canceled, failed orders to that default email.
Now I want to change those addresses to something else. I succeeded changing the failed/canceled orders recipient email addresses, but cannot change the new_orders address.
I have even changed the author of all posts/pages to another admin user, changed the role of the original admin to customer (in case it matters) but still the same.
Any ideas?