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.

Bonus tip:

You can add a subtitle parameter to the end of the Target, e.g.

/Subtitle="Station 2"

and it will be appended to the title of the window.