Can Visual Studio debug stand alone builds?

Title says it all

Yes, it can.

If you build your stand alone with the “Script Debugging” checkbox set to true you will be able to connect the the running instance of your stand alone build.
This is done via the bottom right icon in visual studio. Click on it and attach Visual Studio to the instance.

You can read more about it here: Using Visual Studio Tools for Unity - Visual Studio 2015 | Microsoft Learn