For those who do need the synthetics, I'd recommend polypropylene WAY before polyester. Polyester doesn't wick sweat at all, plus it gets pretty staticky.
Velo has a good list, but it's a long one. I think the top two investments for someone starting off and building their wardrobe would be a wind blocking jacket or vest, and a good pair of well-fitting gloves with wind blocking on the back and grippers on the fingers and palms. That last is important ... you really don't want to not be able to hold onto your brake levers when your hands are stiff anyway.
Most other things you can either transfer gear from other sports/walks of life (like warm tights worn over your cycling shorts, base layers on top, a lightweight knit cap or balaclava for under your helmet), or use a low-rent solution until you can afford the real thing (like plastic produce bags between your socks and shoes, which really work amazingly well in place of shoe covers or winter boots).
Last edited by OakLeaf; 11-04-2013 at 11:02 AM.
Speed comes from what you put behind you. - Judi Ketteler