Gomes's mother sent her to modelling classes at Linda-Ann Model Academy in Perth suburb Midland at the age of 13. There her acting led to a modeling contest and the start of her career. In 2004, she signed with IMG Models after moving to New York City. She has avoided Paris and Milan and done extensive work in most of Asia's major markets — including Tokyo, Seoul, Hong Kong, Beijing, and Shanghai — where she feels mixed heritage Models are more successful. According to Diane Smith, senior Editor of the Sports Illustrated Swimsuit Issue, she is regarded as a "nontraditional" beauty and in her Australian homeland she is regarded for her multiracial background.

In 2005, Gomes moved to New York City and was a flatmate of Gemma Ward. She formerly attended La Salle College. She continued to live in New York at the time of her Swimsuit Issue debut in 2008 and as late as 2011. Gomes' mother was born in Hong Kong, and grew up in Singapore, and her father is from Portugal, and spent time in Paris. Both immigrated to Australia in the 1970s.

Gomes has enjoyed much success through South Korean advertising campaigns. In 2007 she appeared in advertisements for Hyundai Sonata. The following year, she appeared in an advertisement for LG Cyon Bikini Phone, in which she promoted the split screen cellphone wearing a two-piece bikini, under the tagline "Touch the Wonder." This ad campaign is credited as having pushed Gomes to stardom in South Korea. Her popularity grew, and by 2013 between her spokesmanships and Korean television show appearances, she had reached Celebrity status.

In 2008, she was part of a record group of seven "rookie" Swimsuit Issue Models, along with Quiana Grant, Melissa Haro, Yasmin Brunet, Melissa Baker, Jeisa Chiminazzo and Jarah Mariano. That year, she was featured in a bodypainting layout as a canvas for bodypaint Artist Joanne Gair. By the time of her fifth consecutive Swimsuit issue, she had surpassed all Models of Asian heritage.

Before Gomes began modelling in Midland, she appeared as an extra at age 10 on the Australian miniseries Bush Patrol, which led to modelling. While she lived in New York City, she studied at the Stella Adler Studio of Acting. Her Chinese-Portuguese heritage has contributed to her popularity in the Asian market, and in 2009, her reality TV-show My Name Is Jessica Gomes was launched on the English language South Korean television network On Style owned by On-Media. In the shows second season it chronicled her time in New York. She is regarded as a Choreographer and made her dancing debut in the Korean version of Dancing with the Stars on 10 June 2011. She placed third that season.

Gomes has a variety of East Coast Hip Hop connections. In January 2012, Gomes was revealed as the voice behind saying the name of Rick Ross's label Maybach Music Group at the beginning of certain tracks that the company produces. She is "name-checked" in the Kanye West GOOD Fridays song "Christian Dior Denim Flow". Gomes participated as a Celebrity driver in a promotional Celebrity challenge racing event by Mazda associated with the 2013 Australian Grand Prix. Gomes also starred in Z.Tao's music video "Crown".

Beyond her South Korean success, Gomes has appeared in Vogue, Teen Vogue, Glamour, American Glamour and Victoria's Secret catalogue, has modeled for DKNY Jeans, Garnier, Levi's, Motorola, Urban Outfitters and Victoria's Secret, and appeared on the cover of Biba. She signed with Estee Lauder as the face of Sean John's Unforgivable fragrance. She has been featured in ads for Jay-Z Rocawear. In 2009, she was in a Cass Beer ad campaign with Lee Min Ho. She was the Maxim Cover girl for November 2011. On Friday 22 March 2013, Gomes was announced as the fashion ambassador for Australian Retail giant David Jones Limited, replacing Miranda Kerr and joining Megan Gale, Jason Dundas, Montana Cox, Gai Waterhouse and Emma Freedman. That July, she debuted for Jones on the runway. After Gomes became the face of Enprani Cosmetics, she launched a lip gloss named Gomes Pink. Gomes has also shot editorials for the Australian and Vietnamese editions of Harper's Bazaar and modelled for the cover of Cleo.

By 2015 she had appeared in eight Sports Illustrated Swimsuit Issues (2008–2015).