I have read that Drylok is pretty inert. People use it for custom backgrounds in both aquariums and vivariums. You can mix non-toxic pigments or acrylic paint into it (to tint it) as well.
I think the acrylic coating is key to a long term fish safe paintjob. The guys on that show "Tanked" have coated payphones and sports memorabilia, etc and put it in tanks. However, what's good for TV is seldom realistic but something encapsulated in acrylic should be straight.another option would be to paint the rock with acrylic paint and then use a spray paint like Krylon UV Resistant Acrylic Coating