If you'd like to add a path to the %PATH% environment variable, that's easy:
PS> $env:path += ''
But how would you remove a path? Here's a clever way:
PS> (($env:path -split '') -ne 'C:\Windows\system32') -join ';'
To better understand the technique used, check out this part first:
PS> $env:path -split ''
It will separate the paths in %PATH%. Next, -ne will return all paths that do not match the one you want to get rid of. Finally, -join adds these parts back to a semicolon-separated list.