Note: This option is not available on the latest version of Skype. If you are like me, who used two Skype account, I would recommend using the older version of Skype.
If you have two skype accounts and would want to have both the skype accounts available on your PC, here is a simple trick. First open the skype application as you always do and login with your first account. Now use this path on your windows explorer address bar or on your command prompt:
This location may change as per your Skype file location. But make sure you add "/secondary" at the end. This will open up a new skype application on which you can login using your other skype login.
You can open as much of this as you like 🙂