I've never made a cake in a can - but my Mom used to always make pumpkin bread in a can. Just made sure to grease and flour the can REALLY good. It should fall out, after you let it cool for about 10 min. just like any cake pan. If not, just cut the bottom off the can with hand held can opener and give a gentle push.
Hope this helps. 
They put a plastic coating on the inside of all food cans now, you can't see it - but it IS there and it IS toxic. To get rid of this you must burn it off with flames, an oven won't get it all off. You need to stick your cans on an open fire - you'll see the stuff peeling off the insides in a fairy short time. If you don't do this the stuff will leach into your cakes and it is nasty toxic stuff. One way to avoid this problem is to cook in cans that are meant for cooking in - for example you can buy sponge puddings in cans that you're meant to cook in the can.
Are there any cans you can use. I had planned on using this method for an upcoming Thomas the Tank engine cake??????
Great tutorial from marialovescakes:
http://www.cakecentral.com/cake-decorating-ftopict-10273-soup.html
Instead of baking in a can why don't you use a biscuit cutter or a round ateco cutter to cut circles of cake out of a sheet pan than dowel them?
Or you can buy 2" flan or cheesecake rings tape them together to make a tower and bake that way if you want the investment.
when I bake in cans (especially since most cans have little ridges in the sides of them) I spray them and line them with parchment paper....jsut to be on the safe side to avoid sticking! I never knew about the plastic on the inside of the cans.....wonder if the parchment protects from this??
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