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I don't think that there is a definitive difference, unfortunately. From what I understand, PCOS is a diagnosis of exclusion and NCAH is one of the things that must be excluded. Both have symptoms of excess androgens and irregular periods. To diagnose NCAH (at least the 21 hydroxylase variety), you should have a 17 OHP level that has a baseline level over 200 and goes over 1000 on an ACTH stimulation test. Other than that, the symptoms can be the same and you can have both, to make it more confusing. I've also been told that 17 OHP can be high in PCOS, but I've never found out how high.
However, PCOS is typically associated with cysts on the ovaries, insulin resistance, LH level significantly higher than FSH level, overweight with excess weight around the middle, infrequent heavy periods, high estrogen, and low SHBG. Having several of these signs would point toward PCOS as a diagnosis, but none are necessary, according to current medical guidelines, as far as I know.