The biggest problem is getting a strong grip on the post itself. They're round and smooth and slippery.
Use the seat clamp or a clamp piece from a junk seat. You can put the clamp into a vise, or put a junk seat on it really tight and put that in the vise, and use the FRAME for leverage- twisting and pulling the frame off the post.
Even with all these things, and PB Blaster at my disposal (GREAT stuff, we use it in my paper mill where EVERYTHING is rusted solid), I had one that would NOT come out. I had a '68 Stingray that had been ridden in mud (maybe underwater? I dunno) as a BMX bike. The post was most of the way down and stuck bad. I even drilled into it through the bottom bracket, with the frame all stripped, and tried to drive it out with a punch from the bottom! No luck.
I ended up with it clamped up, wrapped in rags of course, held in an industrial floor-model drill press, and a 13/16" extra long drill bit way down inside the frame to remove it. I had probably 10 or 11 inches of post to remove. Ugly. But I had tried for a year to remove it some other way. Even used a bare hacksaw blade down the inside... cut a couple inches but to no avail.
I saved the original paint though...
--Rob