To read a Windows environment variable in PowerShell, simply use the prefix "env:":
PS> $env:windir
C:\Windows
PS> $env:USERNAME
Tobias
Actually, "env:" is a drive, so you can use it to find all (or some) environment variables. This would list all environment variables that have "user" in its name:
PS> dir env:\*user*
Name Value
---- -----
USERPROFILE C:\Users\Tobias
USERNAME Tobias
ALLUSERSPROFILE C:\ProgramData
USERDOMAIN TobiasAir1