Thanks for spotting this I was about to add strings thinking the same as you that they'd get added to end of collection. It appears the params are:
msg.to.Add(<MailAddress>) adds MailAddress to the end of the collection
msg.to.Add(<string>) add a list of emails to the collection
Slightly different actions depending on param type, I think this is pretty bad form i'd have prefered split methods AddStringList of something.