I have silpats (the sheets) and muffin pans in silicone. I LOVE them.
Definitely pay attention to the temperature warnings, though. At Christmas, I unthinkingly put my roast potatoes in a 525F oven with a silpat liner on the rack... and it was bad. The potatoes were fine, though, no taste of anything but potatoey goodness. (The silpat wound up in the trash once it cooled off a bit, it was melted.)
And I've never had a problem with my muffin pans releasing (or browning). I got them originally because I make DH egg muffins for breakfasts sometimes (scrambled eggs and meat/cheese/veggies), but getting them to release from Teflon was a joke, and can't use paper liners either. They pop right out of the silicone pan with nary a mess. I do wash the pan between, but just to get the grease off, nothing sticks to it.
Cookies pop right off of the silpats, as do cream puffs, cheese toast, for some reason I'm drawing a blank on all I use them for... but you can even melt cheese on one, let it cool and it'll pop right off, no scrubbing needed. Anything that you'd put on a sheet pan but not cut on the sheet pan can be baked with a silpat (since you can very easily cut right through a silpat). They can be a bit of a pain to wash, since they're so floppy, but I just flip the sheet pan over and put the silpat on the back of it and wash it that way. They really can't go in the dishwasher.
There is a difference between brands, though. Not all silicone is created equally. A cheap silicone pan is still a cheap pan. And you definitely have to put it on a sheet pan. My muffin pans go onto a sheet pan before filling, or I'd never be able to move them (made that mistake just once). They do sell silicone muffin pans with racks so that you don't have to put it on a sheet pan. I don't think I'd use a silicone pie pan though, just because of the weight of the pie filling... I've looked at bundt pans, but I'm happy with my glass one. I wouldn't mind a silicone (round) cake pan though.
If you're buying silpats, pay close attention to the measurements. The wrong size sheet just doesn't work very well. The right size should be maybe 1 inch smaller than the outer measurement of your pan in both directions. If you can buy them locally, I highly recommend taking your pan into the store with you to get the right one.