Saves work like in previous Bethesda games, they all go into \Skyrim\Saves folder. The Steam account doesn't matter, the game only saves in that directory. Also, Skyrim doesn't have Steam Cloud enabled for saves, so the saves can only be accessed from the computer that the game runs on. Of course you can copy the files to a thumbdrive and transfer them between computers like that.
But you can separate saves of each character on PC by adding "SLocalSavePath" line under General section of the Skyrim.ini file, like so:
[General]SLocalSavePath=Saves\CharacterName\
Why Bethesda didn't include ability to change that from the game in their "new" engine i do not understand
