I've experimented with different silks, and different synthetics. The problem with silk, it's hard to find a super tight weaved version of it that will be more truly windproof, whereas if one buys some Quantum or M50, or what not, you know it's going to be quite wind-resistant to near windproof. I've yet to see a silk fabric that is as wind resistant as these super tight weaved synthetics. This is one of the reasons why silk is not used as a liner for Down sleeping bags or quilts, because most silk fabric is going to let out feathers (especially) and some down.
So yes, that's personally what i would do, is to put a layer of silk together with a very light weight and tight weaved synthetic and put the silk side on the skin. It will be a bit warmer with two layers since more air is trapped. Silk btw, is a somewhat unusually warm fabric for the weight and this is because it's often very fine fibers which are triangular shaped and protein based. The combination of this, makes it warm for it's weight and thinness though it's not a miracle fabric by any means. Fine/high quality silk is actually warmer than Merino on a weight to weight and thickness basis, i think.
It would be much heavier, but you could also look into "raw silk", which is almost more like a woolen fabric, much thicker and heavier, but quite warm. It's less durable than woven silk though. I'm not sure how wind resistant it is, i have some and will do some breath tests and get back to you. A truly wind resistant fabric is somewhat hard to suck air through.