The principal folate in most cases is 5-methyltetrahydrofolic acid. This can be measrued by hplc with fluorescent detection. This method of mine has been used (sometimes modified) it works fine.
3. Leeming R J , Pollock A , Melville L J and Hamon C G B "Measurement of 5-methyltetrahydrofolic acid in man by high performance liquid chromatography" Metabolism, 39, 902- 904 (1990)