I tried it on Windows 7. So here it is.
Go to C:\Program Files\Microsoft SDKs\Windows\v6.0A\Bin>
Run the command
C:\Program Files\Microsoft SDKs\Windows\v6.0A\Bin>makecert.exe -n "CN=PowerShell Local Certificate Root" -a sha1 -eku 1.3.6.1.5.5.7.3.3 -r -sv root.pvk root.cer -ss Root -sr localMachine
You will be prompted to create PrivateKey Password
Following which you will be required to enter the Private Key to successfully create the certificate.
type mmc, and in the console, add (Ctrl+M) Certificate

Under trusted root certifications you should be able to see the PowerShell Certificate you created for code signing.

now run this command
C:\Program Files\Microsoft SDKs\Windows\v6.0A\Bin>makecert -pe -n "CN=PowerShell User" -ss MY -a sha1 -eku 1.3.6.1.5.5.7.3.3 -iv root.pvk -ic root.cer
and you will be prompted to enter your password again.

Now in PowerShell to verify your certificate type the following command , and you should see some thing like this.

Here is the final fun.. that uve been waiting for.
in my case I had a simple ps1 file which needed to be signed, and I signed it using the command

you need not be in a specific directory to sign your code. Its your option of where ever u wana be, like in Starbucks etc.