As Christian said, LV 32 bit will always report it is running on a 32-bit OS.
If you are just trying to determine if you are on a 64-bit OS, then you need to check two things. The architecture, and WOW64. Look at this post. The ZIP file I posted includes two files in the WINAPI directory. One checks for WOW64 and the other checks for architecture. If you know you will always be running 32-bit LabVIEW, then you can just check for WOW64. If you might update the code to LV 64 bit at some point, you will also want to look at the architecture, because 64-bit LabVIEW will not report it is running WOW64.
Look at the last post in the threa di linked for further instructions as to the VIs to use to determine if you are running on a 64-bit OS.