Just use water or your spit to smooth it out or else you get problems like the guy above me.
heh >.<
Water is useless and will just drag the silicone. Saliva works a treat but it'll only encourage mould growth.
A small squirt of fairy liquid in some water is the best thing to use. If doing a thick bead of silicone then an old wooden peg sanded smooth and soaked in fairy/water mix overnight will get a perfect finish.