Its very simple actually. Just follow the below steps and you will be logged in into two account simultaneously.
How to use two Skype Accounts at the same time
1. Press the Windows
and R keys on your keyboard at the same time. Run window will open.
2. If skype is installed in “Program Files (x86)” folder, in run window, type
%programfiles(x86)%/skype/phone/ and click OK
If it is installed in “Program Files” folder, in run window, type
%programfiles%/skype/phone/ and click OK.

3. Right click on Skype file and select Send to > Desktop (create shortcut). It will create shortcut on Desktop for skype.

4. Come to Desktop. Right click on Skype shortcut and select Properties
5. In Property window, select Shortcut tab. In the Target field, add space and then /secondary at the end of the path. It will become one of below as per your folder structure.
“C:\Program Files (x86)\Skype\Phone\Skype.exe” /secondary
“C:\Program Files\Skype\Phone\Skype.exe” /secondary

6. Click Apply and OK.
Now, whenever you double click on Skype shortcut icon, it will open new window of skype application.
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