How do I program a new RKE transmitter to the vehicle if I have two existing recognized transmitters?

Place the two recognized transmitters in the cupholder, then remove the key lock cylinder cap on the driver door handle, insert the new transmitter's key into the cylinder, and turn it counterclockwise to the unlock position five times within 10 seconds until the DIC displays READY FOR REMOTE #2, 3, 4, ETC. Place the new transmitter into the transmitter pocket in the center console, press ENGINE START/STOP, then remove the transmitter and press K or Q. When all transmitters are programmed, press and hold ENGINE START/STOP for 12 seconds to exit programming mode. (Page 33-34)

From the official Buick Enclave manual, page 33

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