Hi Carel,
Is the people picker in the form or just the list? If it's not in the form, maybe the namespace isn't either. Just adding it to the form should be a good test of that.
In general, the data source the people picker gives you is not easy to use for other purposes (such as workflow). I recommend, just defining your own structure and call UserProfileService to populate the value. Especially, if you don't need more than one person, that is going to be far simpler. Check out Clayton Cobb's UserProfileService blog for how to do that.
To check membership, you don't need a double eval. You should be able to do this with a straight xpath on the secondary data source. Does the secondary data source contain all of the items? If so, should be straightforward but tricky. Jimmy Rishe or Hilary Stoupa would be good people to reach out to when it comes to tricky xpath.
Good luck,
P