So why are cave fills not available for open water, NDL divers? For the most part, because they really aren't needed. If you are staying within NDLs, getting that extra gas shouldn't do you a whole lot of good.
I own a set of LP 85s that I expressly bought for sidemount cave diving, and they have had cave fills for that reason. I also use them backmounted for OW, NDL dives. The South Florida shop I use for fills used to give me something close to cave fills on many occasions, and I used to get back on the boat after a long OW dive with oodles of air. This past year (I am only there in the winter), procedures changed, and I no longer get those big fills. They still overfill them a tad (about 2900 usually), but I am still getting back on the boat with oodles of gas.
It is to a large degree also true of typical OW tech dives. I have done such dives in South Florida using LP 108s, and I absolutely could not get them filled past their rated pressure; in fact, the shop I used then often would not even fill them to their rated pressure. It was still enough gas for the dives we did.