But suppose you were running this 2-channel validation constantly, for people with both routine and exceptional needs. You'd be getting fresh information, in exactly real-need/real-disorder proportions, from both the traditional and new tests, in the cheapest and fastest way possible.
Storing 'baked-sample' blood, or doing extra tests against people who weren't otherwise needing tests, couldn't possibly be as representative. Diverting a few drops from tests that are already going through the traditional process, for research/calibration purposes, is likely already authorized by existing patient relationiships. Your "n" for analysis, across any disorder or rare test, would quickly exceed what's "recruitable" for some formal study.
Look at the list of Theranos partners/customers who have brought them to "cash-flow positive": hospitals, drug companies, insurance companies, and the US military.
It's naive to the ways of industry R&D to assume that such constant cross-validation hasn't been (and isn't still) happening.