Appropriately you may know the compound properties or some basic assumption about the unknown compound? like acidic?basic? organic? like this info you may know means perfectly possible to do.
Only for GC-MS analysis means for isolated unknown compounds best method is:
If your sample is bio sample or expensive means, the clear efficient method for all compounds is:
10mg of sample and 0.2ml of HexaMethylDiSilane, and 1ml of pyridine, finally catalyzed with 0.1ml of trimethylchlorosilane, allow the reaction for just 5mins.
if just simply u need to silylate means,
Your sample with HMDS/pyridine just sake it and keep it for 5mins and then you analyze.,
Dry silylation also available that is basic your well known.