Try this? (tested on v4.6.4, but use with caution)
Code:
REPLACE INTO xcart_config VALUES ('users_department','Users department email address','first@email.com,second@email.com','Company',320,'text','','','text','');
REPLACE INTO xcart_config VALUES ('orders_department','Orders department email address','first@email.com,second@email.com','Company',330,'text','','','text','');
REPLACE INTO xcart_config VALUES ('support_department','Help/Support department email address','first@email.com,second@email.com','Company',340,'text','','','text','');
If it doesn't work, try separating the email addresses with semi-colons instead of commas.
To reset, on each line change...
to...