This SQL patch does the trick... (v4.4.x - v4.5.x)
Code:
REPLACE INTO xcart_config VALUES ('orders_department','Orders department email address','first@email.com,second@email.com','Company',330,'text','','','email');
The others available are...
Code:
REPLACE INTO xcart_config VALUES ('site_administrator','Site administrator email address','first@email.com,second@email.com','Company',310,'text','','','email');
REPLACE INTO xcart_config VALUES ('users_department','Users department email address','first@email.com,second@email.com','Company',320,'text','','','email');
REPLACE INTO xcart_config VALUES ('support_department','Help/Support department email address','first@email.com,second@email.com','Company',340,'text','','','email');
The caveat is that where emails are displayed elsewhere in your store, it will show both, so you may need to adjust / hard code the order invoice etc.