I think there are two defaults: a global default and a contact-specific default.
The global default is used when you send an e-mail to a contact you haven't e-mailed before. The contact-specific default is based on the previous e-mail you sent to that contact. Try sending the contact in question an e-mail from the preferred e-mail address and see if that contact's default changes.
That's how it works that way on my TMO 8700g anyway.
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