Duno's path into motorsport was unconventional. She was introduced to racing through an invitation to a driving clinic by a car club in Venezuela and did not begin competing until she was 24, relatively late for a professional career. Prior to racing, her background was primarily academic: Duno holds master's degrees in organisational development, naval architecture, maritime business, and marine biology, and worked as a naval engineer before turning to motorsport.
Duno began racing in Venezuela in 1996, finishing second in the Venezuelan GT Championship. In 1998 she placed fourth in the Venezuelan Porsche Supercup Championship. In 1999 she moved to the United States, attended advanced racing schools, and drove in the Barber Dodge Pro Series in 2000. That year she became the first woman in history to win a Ferrari Challenge race in the United States and also won the Panoz GT Series championship.
From 2000 onward Duno built an impressive record in sports car racing. She made her American Le Mans Series debut that year, becoming the first woman to finish on a class podium in that championship. In 2001 she was crowned vice-champion in the LMP 675 class of the American Le Mans Series, scoring four class wins including the Petit Le Mans, making her the first woman to take a class victory in that major international event. She scored another LMP 675 class win at the Petit Le Mans in 2004.
She also competed in the World Series by Nissan in Europe in 2001 and 2003, becoming the first woman to score points in that championship. Beginning in 2004 she raced full-time in the Rolex Grand-Am series, driving Daytona Prototypes. During her time in the Rolex Sports Car Series she earned three overall wins — twice at Homestead-Miami Speedway and once at Le Circuit Mont-Tremblant in Quebec — making her the first woman to win overall in a major international sports car race in North America. She accumulated seven podium appearances, ten top-five finishes, and eighteen top-ten finishes across the series.
For the 2007 24 Hours of Daytona, Duno teamed with Ryan Dalziel, Darren Manning, and Patrick Carpentier. The car finished second, making Duno the highest-finishing female driver in the history of the race, surpassing Ernesto Soto's fifth-place result from 1982 as the highest-placing Venezuelan driver at Daytona.
Duno entered the IndyCar Series in 2007 with SAMAX Motorsport, sponsored by CITGO, running a partial ten-race schedule that included the Indianapolis 500. At the Kansas Lottery Indy 300 in April 2007, she became one of three women — alongside Danica Patrick and Sarah Fisher — to start the same race in North American open-wheel history, the first time that had ever occurred. She competed in the 91st Indianapolis 500, where three women appeared in the same 33-car field for the first time; she crashed out on lap 65 and finished 31st.
In 2008 Duno signed with Dreyer & Reinbold Racing for an eleven-race schedule. She qualified for the Indianapolis 500 on the second qualifying weekend and finished 19th, the highest-finishing female that year as Danica Patrick and Sarah Fisher finished 22nd and 24th respectively. She remained the only woman still running at the race's conclusion after the other two were involved in accidents.
Duno returned to Dreyer & Reinbold in 2009 for a nine-race part-time schedule. In 2010 she signed with Dale Coyne Racing for a full-time IndyCar campaign, competing in sixteen of seventeen races. She failed to qualify for the 2010 Indianapolis 500, the only race she did not make in her 43-race IndyCar career. That August she was one of five women — alongside Danica Patrick, Simona de Silvestro, Ana Beatriz, and Sarah Fisher — who all qualified and raced in the same IndyCar event, the first time five women had competed together in IndyCar history.
Duno's IndyCar career was not without controversy. She was criticised for running significantly below competitive pace in several seasons, and in 2010 she was parked by officials at the Grand Prix of Toronto and at Iowa Speedway due to lack of speed, subsequently placed on probation by IndyCar for consistently poor performance.
Duno made her stock car debut in the 2010 ARCA Racing series season opener at Daytona. She competed in the 2011 ARCA season for Sheltra Motorsports, finishing 18th in driver points despite the team ceasing operations mid-season and then resuming. In 2013 she completed a full ARCA season, finishing seventh in the driver championship standings, the second-highest finish by a female driver in ARCA's 61-year history at that point. Her 2013 season included pole position at Talladega Superspeedway, placing her among only four women to earn pole positions in ARCA history.
In August 2014 Duno signed with RAB Racing for a limited NASCAR Nationwide Series program. She competed at Kansas Speedway and Homestead-Miami Speedway; at Kansas she became the first Hispanic female driver to compete in a NASCAR national series in the United States. She also ran one Camping World Truck Series race at Talladega Superspeedway in 2014, leading two laps.
Through the Milka Way Foundation, established in 2004, Duno engaged in school outreach programs across the cities she raced in, encouraging academic achievement among young people. In 2008 she appeared in the Warner Brothers film Speed Racer, playing the role of Kellie "Gearbox", and published a bilingual children's book, Go, Milka, Go!, which received the Best Young Adult Sports/Recreation Book award at the 11th Annual International Latino Book Awards in 2009.
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