Can’t block spam email from a very specific email account on hotmail

Use the Generic Test for Unsolicited Bulk Email (GTUBE). It's a standardized spam signature used precisely for testing spam filters.

Put this in the body of the test email:

XJS*C4JDBQADN1.NSBN3*2IDNEN*GTUBE-STANDARD-ANTI-UBE-TEST-EMAIL*C.34X

and it will force it to be recognized by Gmail as spam.

You shouldn't... Any chance your wife occasionally sends out mails with groups of people listed in the CC: field? Does she, you, or any of your contacts have links to the rest of you on a social networking site where email addresses can be seen? There are hundreds of ways groups of people can be tied together using publicly available information, or simply even one of her contact's machines all virused up and reporting email groups back to spammers...

This is assuming, of course, that she doesn't keep sensitive information in her contact list stored electronically. If you'd be nervous about printing it out and letting a restaurant full of people skimming over the information there, then yes, be worried.