Create a shortcut to Skype.exe and place it on Desktop or start menu. Use a name the will help you clarify which account is which. Start Skype using this shortcut and setup your first account.
Then create another shortcut to Skype.exe with a different name. Open the “Properties” of this shortcut by right-clicking on it. In the “Target” text field of the properties dialog box, append ” /secondary” (do not use the quotes) to the Skype.exe path that is already there.
For example: “C:Program FilesSkypePhoneSkype.exe” /secondary
Now you can change icons in order to identify easier each account