To upgrade an existing copy of Vista to a different version you have to use the Windows Anytime Upgrade feature built into the OS.
Details of the upgrades are available here. And according to that page it costs £112.03
There is also an FAQ page here. And a 32bit to 64bit FAQ here.
However, if you own a 32bit copy of Vista you are entitled to a 64bit copy of the same version of Vista. Only Ultimate comes with both versions in the box though so you have to order the 64bit version of Premium if you wanted to stick with that one. Go to this link and it gives details on how to order a 64bit DVD using the product key you already have for Vista.





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