Hi. Congrats on getting your bike! I've done some long outdoor bike rides myself including a few centuries.
There aren't really different ways to set your bike up in terms of output, etc. it's more about which classes you choose.
If you're looking for a structured program on Peloton I would start with the Power Zone training programs and once you get into it start doing some of the longer ones - 60 or 90 minutes. You'll want to get used to having your heart rate up and maintaining some level of output for long periods of time.
If you haven't done long rides before you'll definitely want to build up the amount of time in the saddle on the bike you're going to use. An outdoor bike, especially a road bike has you sitting on a small hard seat and hunched over so you're body needs to get used to being in that position for hours at a time.
Here's a blog post I saw about someone who used PZ to train for an outdoor ride.
Peloton Member Kevin Martin used Peloton Power Zone rides and the Peloton Bike to train for the legendary Leadville Trail 100 MTB in Colorado.
blog.onepeloton.com