Photoshop CC installs a 32 bit exe and a 64 bit exe on your system. Use the 64 bit version under Program Files. or type Photoshop CC in the Start Menu's search box. You should see Photoshop CC 64-bit in the list.
The 32-bit version is the one with the 4 GB ceiling, but some users have legacy 32-bit plugins and drivers that have not been updated and won't work in the 64 bit version.