I like Patagonia capilene layers. On tour I live in 2 capilene 2 T-shirts that I rotate, and a capilene 4 long sleeve that functions as a sweater. Both pieces are really comfortable, dry fast, insulate well, and don't look too techy or outdoor activity specific. They do fairly well in the smell department too, they don't get the wet dog effect that wool does, although they do probably smell more than cotton does dirty. For me they are perfect on and off the bike.

For shorts I like the Rapha touring shorts. The cut is nice, it's not super baggy like most mountain bike shorts, but it's slim enough to function well when riding.

I like to have garments that work on and off the bike. That way, I can ride all day in 1 set, and change into the clean set at night and wash the riding set. Then the next morning I can still wear what I wore at night while riding, so the washed set has time to dry if necessary.