1.Find the Skype.exe file
From the Windows taskbar, click Start > Run (or press the Windows The Windows key. and R keys on your keyboard at the same time). In the Run window, type the following PATH and press OK:
if you’re running a 32-bit operating system,you please use this path
C:\Program Files\Skype\Phone\
If you’re running 64-bit operating system,you please use this path
C:\Program Files (x86)\Skype\Phone\
2.Right-click the file and select Send to > Desktop (create shortcut).
3.Locate the shortcut on your desktop, then right-click it and select Properties.
4.In the Target field of the Shortcut tab, add /secondary to the end of the path.
The Target field should now be
"C:\Program Files\Skype\Phone\Skype.exe" /secondary
Copy and paste that there just as it is. There is a space before /secondary
5.Click Apply and then OK button.
6.You can now start a new instance of Skype every time you double-click the new shortcut.
Simple Method
From the Windows taskbar, click Start > Run (or press the Windows The Windows key. and R keys on your keyboard at the same time). In the Run window, type the following command (including the quotes) and press OK:
For 32-bit operating systems:
"C:\Program Files\Skype\Phone\Skype.exe" /secondary
For 64-bit operating systems:
"C:\Program Files (x86)\Skype\Phone\Skype.exe" /secondary
If you get an error message, copy and paste the exact command from this page and try again.
How to Quit a Skype account ?
1.Goto Taskbar ,Near time you can see multiple skype icons
2.Right click a skype icon
3. Click on Quit
4.System will ask "Are you sure want to quit" -Then click on Quit button
I have personally tried this method in Windows 7 ,32 bit PC ,It is working fine
How to Quit a Skype account ?