I was trying to use skype with tw credential a t the same time and i found this great way to do it.
First, Create a new Windows user by going to the Control Panel and Clicking on “User Accounts”. Choose “Create a new account” and follow the steps to set permissions.
Skype also suggest setting a password for the new user by clicking on the newly created User and choosing the Set Password option.
The new user will also require admin rights on your PC.
Next, create a shortcut to Skype or make a copy of the Shortcut that is already in the start menu. Right click this new shortcut and choose properties. On the bottom of the first page will be a button labeled “Advanced…”. Click this button and select “Run with different credentials”. Select OK, and then select OK again to close the Properties dialog.
You’re all set. Whenever you use this new shortcut it will ask for a Windows username and password. Enter the username and password of the user you created earlier by choosing “The following user:” option. Click OK and you’ll have a second instance of Skype. It will require that you log in with your Skype username and password the first time.
To help automate the ‘run as’ trick you can create a second desktop icon for Skype and modify its properties. Click the advanced button and check the box ‘run with different credentials’. After clicking on the modified icon it will ask you to sign in as another user. Changing the icon graphic also helps ensures you click on the correct icon.
If you have multiple USB headsets or USB Phones you should be able to setup both instances of Skype to use a different sound device