I would advise you taxi direct to Higuey from the airport, 45 min. It would save the added taxi or bus expense should you decide to overnight in a PC/Bavaro hotel in order to connect with the 7 am Bavaro bus to the capital or choose to travel to Higuey to catch the hourly express.
In Higuey you can opt to stay at the Barcelo Naranjo or the Don Carlos. The bus station is in front of the cathedral and is a little more than a city block walking distance from the Naranjo and about 3 city blocks from the Don Carlos. The express buses run hourly from Higuey to the Capital.
Barcelo Naranjo
http://bookings.hotels.com/hotels/ho...ce=&country=DO
Hotel Don Carlos
J P de León
Higuey
(809) 554-2713
Regards, PJT