Hi,
I don't think that's possible after reading a related topic here
Roman numerals would not be able to cope with subsections, as you can't write something like 1.2.1 as roman numeral. Also, more theoretically, roman numerals only go up till about 4000, so you can't convert large numbers (though this would not be an issue in a book, as there are likely not that many chapters).
It seems the only solution is to build custom css, js or latex depending on the knitting, but that's too advanced for me Maybe someone else knows how to do that.
PJ