What you're looking for is a listing of the High Altitude Preferred Routes. I'm sure that they are probably available on the web, but that's not were I personally source them - I use a flight planning program that stores them in its database.
It's Monday morning and I typing this in my hotel room here in Orlando. Yesterday, I flew from our homebase in Klamath Falls, Oregon to Atlanta, then on to Orlando. You are correct about the routing from Atlanta to Orlando. I filed the preferred route you mentioned and was "cleared as filed". The preferred routes are set up to expidite traffic between many (but not all) city pairs that have a lot of traffic volume. (There are also Low Altitude Perferred Routes.) Preferred Routes are commonly used, but not always mandatory - the controllers have a certain amount of latitude here. Personally, I only file them when I'm flying between two cities that are comparetively close together - like Atlanta and Orlando. If I'm going coast to coast, I will file the initial part of the route - about as far as I figure it will take me to get to either FL390 or FL410,depending upon my direction of flight, then I file direct to an appropriate initial fix on one of the STARs that serve the particular airport.
Corporate pilots don't always fly between airline hubs. Most airports don't have perferred routing between them. What the larger airports frequently have are departure and arrival gates that controllors use to route aircraft in and out of the airports. If airports have DPs (SIDs) and/or STARs it's simply a mater of choosing an appropriate DP and STAR then file DIRECT between them. If the airports have neither DP or STAR, we simply file direct.