Am I correct in assuming that if a program's folder resides in C:\Program Files (x86) that it runs as a 64-bit program?
no, in general a 32 bit program will install to the "Program Files (x86)" folder, and 64 bit in the "Program Files" folder.......but that does not always mean the program is 32 or 64 bit....
For example, I run many chess programs, and the GUI is 32 bit and installs in the x86 folder, as expected, yet it has sub-directories for the 64 bit chess engines under the x86 root for the GUI....in this case, both 32 and 64 bit are running under the x86 folder....
the best way to tell is use task manager, and look at your processes: a 32 bit process will have "*32" after the image name.