Hewitt lost serve four times Tuesday in falling 6-4, 6-4 to Goldstein, who is ranked 86th in the world.
The 6-4, 6-4 score came up often in the first round of the hardcourts tournament, with fourth-seed Robby Ginepri stopping Justin Gimelstob by that score and sixth-seeded Tommy Haas not even facing a break point his 4-and-4 victory over Wayne Arthurs.
Seventh-seeded Slovakian Dominik Hrbaty advanced by topping American qualifier Zack Fleishman 7-5, 7-5. Other wins Tuesday were posted by Swiss qualifier George Bastl, American wild-card entrants Scott Oudsema and Sam Querrey, Russian Marat Safin and Germany's Lars Burgsmuller. Only Burgsmuller needed a third set in winning.