I am aware of some the obvious gains of the x64 architecture (higher addressable RAM addresses, etc)... but:
You are already aware of the x64 advantages (most importantly the increased RAM size) and you are not interested in any, then don't port an executable (exe). Usually performance degrades after a port, mainly due to the increase in size of a x64 module over x86: all pointers now require double length, and this percolates everywhere, including code size (some jumps, function calls, vtables, virtual invokes, global symbols etc etc). Is not a significant degradation, but is usually measurable (3-5% speed decrease, depends on many factors).
DLLs are worth porting because you gain a new 'audience' in x64 apps that are able to consume your DLL.