The entire 382-km (237-mi) coast from Punta Sam near Cancún to the main border crossing to Belize at Chetumal is traversable on Carretera 307 -- a straight, paved highway. A few years ago, only a handful of gas stations serviced the entire state of Quintana Roo, but now -- with the exception of the lonely stretch from Felipe Carrillo Puerto south to Chetumal -- they are plentiful.
Good roads that run into Carretera 307 from the west are Carretera 180 (from Mérida and Valladolid), Carretera 295 (from Valladolid), Carretera 184 (from central Yucatán), and Carretera 186 (from Villahermosa and, via Carretera 261, from Mérida and Campeche). There's an entrance to the autopista toll highway between Cancún and Mérida off Carretera 307 just south of Cancún. Approximate driving times are as follows: Cancún to Felipe Carrillo Puerto, 4 hours; Cancún to Mérida, 4 1/2 hours (3 1/2 hours on the autopista toll road, $27); Puerto Felipe Carrillo to Chetumal, 2 hours; Puerto Felipe Carrillo to Mérida, about 4 1/2 hours; Chetumal to Campeche, 6 1/2 hours.
Defensive driving is a must. Follow proper road etiquette -- vehicles in front of you that have their left turn signal on are saying "pass me," not "I'm going to turn." Also, south of Tulum, keep an eye out for military and immigration checkpoints. Have your passport handy, be friendly and cooperative, and don't carry any items, such as firearms or drugs, which might land you in jail.
Several major car-rental companies service Cancún and have branch offices at the Cancún airport. Renting a car from one of these airport branches will get you the cheapest rates. Most first-class hotels in Puerto Aventuras, Akumal, and Chetumal also rent cars. If you're planning to stay in Puerto Morelos, though, it's better to rent a car in Cancún, as there aren't many bargains in town. In Playa del Carmen, stick with the bigger rental agencies: Hertz, Budget, and Thrifty. If you want air-conditioning or an automatic transmission, reserve your car at least one day in advance. Always include a full insurance package with your rental.