Estradiol valerate gets quickly hydrolised and broken down into estradiol, at the moment of passage in the intestines. The same applies when it enters blood, the ester is quickly cleaved so that essentially, estradiol valerate is the same as estradiol, their pharmacokinetics are similar. This has been confirmed in studies. If that was not the case, we would expect the same dose of estradiol valerate to yield far higher levels of estradiol as compared to estradiol which is not the case. Sometimes, levels end up being even lower on estradiol valerate.
According to Bayer, the estradiol valerate in Progynova is micronized so can readily pass through mucous membranes when taken sublingually because particles are very tiny (i.e. micronized). The only way to really know is take them sublingually, with doctor's approval and then measure levels 1 hour later, compare to taking them orally and 1 hour later.
I personally had similar results (physically and psychologically) on Estrace (micronized estradiol) taken sublingually vs. orally.