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As far as I can tell, what you want to do is not possible in any easy way - since to complete the condition you have to select items from the pick lists.
However, you could sort on Category and People at the same time (Sort Order | Choose Fields and then select Category and People). This will list all of the items with blank categories and blank people at the top, then blank categories with actual people next, and finally those items with category filled in - with or without people.
In my database, I specifically use "_No_People" as a field value, to specify that there are no people in the photo. This would help with your issue, but also helps you distinguish between blank (ie haven't put a value in the field - it needs reviewing) and those actually having no people in them (eg landscapes)
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