Ah, yes - the appointments are completely separate to the Super Priority Service.
Super Priority is offered by UKVI themselves and you add/purchase it at the time of paying for your visa application.
UKVCAS is a third party company which takes biometrics and uploads/submits the documents on behalf of UKVI, so you book and pay for your appointment through them... and the type of appointment you book purely depends on what UKVCAS service you want to pay for (i.e. document checking and/or scanning, out of hours appointment etc.).
Then once you have attended biometrics, if your application payment to UKVI indicates that you have purchased Super Priority they will process the visa within 24 hours/by end of next working day. If you haven't paid for priority, they will put it in the standard 'pile' and process it within 8 weeks.