I recently received an application for a PhD position from someone who is already working as a postdoctoral associate. The difference in fields is not particularly large—I work in chemical engineering and materials science, while the applicant originally is coming from computational chemistry.
So the obvious question is, why would someone want to pursue a second doctoral degree when they already have one in a related field, and why would I, as a potential advisor, want to consider someone interested in doing this? (For instance, it seems obvious that the person wouldn't likely need as much training as a novice, but there would also be the challenge of trying to find such a person gainful employment afterwards.)