My expertise has not been in fondant, however with the rising demand, I am forced to do it. All in all, I am doing GREAT.....however am having to stick with cookie cutter types of lettering etc...I have tried putting a little grease (based on a tutorial I saw), and have tried corn starch (also from a tutorial) and I can not seem to get the fondant to come out smoothly. Any help, tips and suggestions would be GREATLY appreciated :) TIA
In my experience fondant does not work well with silicone molds - I always use gumpaste for that. Also, if the mold used is intricate or in any way "difficult", I pop the filled mold in the freezer for 10-15 minutes before removing the gumpaste. It may make the gumpaste a bit sticky once it reaches room temperature again, but just leave it on the counter for a bit and it will dry out nicely. 
AUse straight up gumpaste, its a lot stiffer, dries quicker and handles better on those inticate designs. Especially tappit letters, they used fo drive me nuts! Elisaber's freezer trick works a treat also! I also found the scribed tool to be invaluable for this type of work.
Good luck!
I use fondant in silicone molds all the time. I only use gum paste for things like flowers that aren't going to be eaten. When using the tappit letters you want to let the fondant rest a for a few minutes, this lets the outside harden slightly. Sweet Wise has a video on how to use the tappit lettering, look under their 'tool videos' and you will find it along with several others. For silicone molds try rolling the fondant in a ball or rope (depending on the mold you are using) and before you put it in the mold lightly dust it with corn starch. Do not put anything in the silicone mold, especially not grease. Then pop it into the freezer for a few minutes and it should come out without distorting the applique. Some molds will not need to go in the freezer such as the beads, the mold bends in half and the fondant will just fall out. Good luck.
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