Locate the PlayIt Live icon on your desktop:
Right-click and drag this and select Copy here to create a copy:
Then right click the new icon and click Properties:
Under General, rename this to, e.g., PlayIt Live - Station 2
Under Shortcut, enter into Target:
"C:\Program Files (x86)\PlayIt Live\PlayItLive.exe" /CustomApplicationDataPath="C:\Station2" /Multiple
where C:\Station2 is a folder where the data for that station will be stored.
Click OK and double-click the PlayIt Live - Station 2 icon to launch PlayIt Live for that station:
You can then repeat this for additional instances.
You can add a subtitle parameter to the end of the Target, e.g.
and it will be appended to the title of the window.