Her induction into the world of women's rights probably began as a student on the campus of The University of Maryland in 1923, where she was studying to become a teacher. She found the rules on campus unfair to woman - rules that prohibited smoking for female students, but not for males, requirements that women in dormitories turn off their lights at 9:30 p.m., while no such restrictions were placed on the men on campus. She deliberately violated the lights-out rule and vigorously defended women suspended for violating the no-smoking rule. However, her involvement with a group of female students who provided secret affidavits to a Washington Post reporter alleging sexual exploitation of the co-eds by the faculty (including seductions and "spanking parties") led to the University's refusal to readmit her the following semester. The resulting scandal brought the resignation of the University President, according to A History of the University of Maryland by Professor George Callcott, and the denial of an education to Ms. Simpson. She sued the University of Maryland for readmission and won the case, but it was overturned on appeal, with the justices noting that this "was a young woman not readily submissive to rules and regulations." However, her experience introduced her to the field of law and no doubt led to her decision to become an attorney at a time when it was almost unheard of for women to pursue such a profession.

Vivian Simpson transferred to George Washington University and later its law school, graduating with highest honors.

She opened a solo law practice in Rockville, Maryland in 1928, at a time when she was the first and only woman admitted to the Montgomery County Bar. She continued to practice law in this state until she was nearly eighty years old, having been joined by her younger brother in 1934, when he followed her footsteps into the profession.

Simpson and Simpson became one of the most highly respected law firms in the state of Maryland, and Ms. Simpson's distinguished career spanned fifty years, during which time she repeatedly broke barriers for women, earning appointments as the first woman attorney for the Board of Montgomery County Commissioners in 1938, the first woman ever to serve on the Maryland Industrial Accident Commission (now the Workers Compensation Commission) 1940-47, the first woman Secretary of State for Maryland in 1949, and the first woman ever to be elected President of the Montgomery County Bar Association in 1949. She retired in 1980.

In 1999, Vivian Simpson was posthumously honored as one of the twenty "Lawyers of the Century" in Montgomery County by the Maryland Bar Association.

Her brother and partner, Joseph Simpson, died in 1976, and Vivian V. Simpson died on August 5, 1987. Her obituary, published in The Montgomery County Sentinel on September 3, 1987 notes: