Meyers, who was brake woman on the sled that won the bronze medal four years ago in Vancouver, piloted the top American entry Tuesday to a combined time of 1:54.89 for two trips down the course.
Williams, whose pushing skills contributed to the fastest start time of the day, is trying to become the first athlete in Olympic history to win a medal at both the Summer and Winter Games. She won a silver medal in the 100-meter dash in 2004 at Athens and was part of a relay gold won by the Americans in London two years ago.
The Canadian team of Kaillie Humphries and Heather Moyse, are trying for their second Olympic gold medal in a row, had the second best combined time of 1:55.12. Jamie Greubel and Aja Evans of the United States were third 1:55.45.
Jazmine Fenlator and hurdler Lolo Jones, who were in the third of the American sleds, were in 11th place.
This is the fourth Olympics in which women have competed in the bobsled. In the previous three the United States has won a gold, silver and bronze medal.
The most recent competitor to earn a medal in both the Summer and Winter Olympics has been Canada's Clara Hughes. She won a pair of bronze medals in individual cycling races at the 1996 Summer Games in Atlanta and also won a speed skating bronze in Salt Lake City six years later.