There is a #glitch of some sort where #follows can get stuck in the "follow request" state, even for accounts that don't normally require follows to be approved.

When this happens, pressing "Cancel Follow Request" and then immediately pressing "Follow" on their profile will get you immediately following them.

I don't know a way to tell these from accounts that really do require that requests be approved, and just haven't approved mine; so I hope that on the rare occasion that I do press Cancel and then immediately Follow on one of those, it doesn't annoy them...