Comma separated should work, but try adding them as separate rows instead to be sure. (see private area)
You shouldn't set the FROM to the entered email address. Many email suppliers will block emails that are "From" them that aren't sent from their servers. You should use a FROM with @yourdomain.com where yourdomain matches the domain of the site sending the email.
You can set the Reply-To email address separately and use the entered value there so that any replies to the email will go to the user that filled out the form.
If the FROM still isn't showing after that. Go to the settings section of the email dialog and check the box for "Use additional headers". Your server may require that to set the FROM properly.
The CC and BCC are set in the include file ("webassist/email/waue_confirm_1.php"). You could add them there manually, but I'd need a copy to give you the lines and syntax.