I had the same inclination when I first started blogging (the source of my referrals). I was noticing that a lot of referred contributors weren't getting accepted at Shutterstock. At least a lot of them had zero photos, so I presumed it was because they weren't getting accepted.
So I wrote a blog post collecting all the advice I could gather about how to successfully get through the admission test at Shutterstock and other agencies. A few months later my referral income more than doubled (not that it was high at that point).
I don't think I'd go the direct contact route. I was in a fortunate position that the source of my referrals (my blog) was also an opportunity to help my referrals all (mostly) at once.
I'd suggest that referrals who are going to produce enough referral income to make it worth your time don't need help anyway. Sure, there's the chance your assistance will make the difference for the next up-and-coming microstock superstar who is currently struggling, but that's a bit of a gamble, especially given you're suggesting one-on-one assistance. Like others have said, I think you'll make more money in the long term shooting instead. There's plenty of resources for your referrals to find their own assistance, and they're not difficult to find.
