I recomend you look up cold weather layering, to get an idea which materials should go where.
Basically synthetic against the skin is best as it keeps moisture off the skin.
Then your warm layer, wool, fleece are good, and your outer shell,
If your sweating while hiking, slow it down,
Take off a layer, open zippers, anything not to sweat.
Then bundle up at your stand.
If you sweat, will just be cold and wet when you do stop.