The answer, it turns out, is quite simple: PowerShell.exe is not a .NET Assembly (had to verify with ILDasm.exe to prove it to myself).
It simply loads modules/dlls into the CLR as needed. The CLRVersion value is reporting the CLR version that PowerShell will use when it loads assemblies. Unfortunately I'm not able to find any good resources that detail the process PowerShell uses to load/interact with .NET code.