I would assume the idea is to replace the current S3 so it can be set to "Not recommended for new designs" as soon as the S31 is ready. Having similar names makes it easier to communicate such a step.
That sounds very plausible.
This choice of name is going to be causing confusion down the road though. The S2 and the S3 have a lot in common, and the S3 can be reasonably seen as an extended version of the S2; the S31 is a completely different chip, i.e. the step between S2 and S3 is much smaller than between S3 and S31...
However, I have now learned that I don't understand Espressif's naming scheme at all. I guess the names are chosen based upon some characteristic (target application/product?) I'm not aware of.
Let's keep looking forward to when the S31 comes and hope that it'll become reasonably available for tinkerers
