This was found here: http://www.unix.com/shell-programming-scripting/12995-perl-emailing-multiple-files-attachment.html
This was really hard to find (google-fu may have been weak) so thought I should spread it around..
Make your message Type "multipart/mixed" and for the attachment:
...
$msg->attach(
'Type' => 'application/octet-stream',
'Encoding' => 'base64',
'Path' => "<some Excel file here>"
);