The Windows folder on PlayOnLinux and Wine do not store your Windows files and/or programs. The Windows folder is used to create a space where all the files needed to run a windows program is located, excluding Windows boot mechanisms and YOUR Windows. It's not the Windows located on your hard disk, it's just a dummy folder and will not hold any of your data at all.
The thing you need to do instead of this is to copy the installed files from Windows to a thumb drive, external drive, CD or whatever or load the disc of the game, or get the installation package from wherever and follow the instructions here.
I highly recommend Wine as an alternative, because PlayOnLinux is actually based off Wine and personally I find Wine so much easier to use and there are many more support pages and documentations to read and discover.
The only advice I can offer to you now is read the documentation! That should've told you everything I just wrote, and use YouTube and Google - because they are great sources.