Simon,
In essence, what PlayIt Live does is makes a continuous audio source from a number of smaller audio files.
If you make your audio the "library" it will play the clips continuously.
The simplest way to make an "online radio station" from this audio is to use the PlayIt Live audio streaming plug in and link that to a shoutcast server ( for example and picked because their website seems to have some useful instructions Shout Cheap http://www.shoutcheap.com/shoutcast/ ).
Having said that, many shoutcast streaming services also have an "Auto DJ" service where you upload your audio to them and they play it out. That avoids you having to have your computer running 24 x 7 and seems suitable for your application.
The streaming provider will generally offer some kind of embeddable player to include in your website.
That would seem to do what you want.
Simon Foy
If I set this up with the audio I want to broadcast on the internet (no music, just voice audio, speeches, debates etc) is there any way to get this software to broadcast it on the net via my own website? So people visiting the site can click "listen" and it will automatically tune into what I've loaded into it?
Sorry but I've an idea of what I wish to do with no experience on how to do it.
Thanks Si