Sampson was born on May 18, 1974, in Bedford, England. She attended the University of Birmingham, where she studied voice with Richard Smart and sang with the choir Ex Cathedra. She made her debut in Monteverdi's L'incoronazione di Poppea at the English National Opera and has appeared in many productions with that company. She has also appeared at the Paris Opera but most commonly performs in concert with leading early music ensembles, including The King's Consort, Collegium Vocale, and the Freiburger Barockorchester. Sampson has also appeared with major symphony orchestras, such as the NDR Radiophilharmonie and Rundfunk-Sinfonieorchester Berlin. She made her solo recording debut in 2004 with a pair of albums on the Hyperion label (her credits date back to the 1990s), one featuring love songs from Rameau's operas and the other of Handel's Ode for St. Cecilia's Day, HWV 76.
In 2005, Sampson recorded a newly discovered Bach cantata, Alles mit Gott und nichts ohn' Ihn, BWV 1127, with Suzuki, then in the process of recording a complete Bach cantata cycle, and she appeared on a number of releases in the cycle. In 2007, her performance at the Boston Early Music Festival production of Lully's Psyché was recorded and earned her a Grammy nomination. She went on to record other albums for the BIS label, home to the Suzuki recordings, in the 2010s, and she has also recorded for Vivat, Harmonia Mundi, and other labels. Although she has focused mostly on Baroque music, she has also recorded music by Charles Villiers Stanford, Hubert Parry, and Francis Poulenc, among other more recent composers. Sampson has appeared on more than 100 albums in all, including a recording of Canteloube's Songs of the Auvergne on BIS in 2021. ~ James Manheim, Rovi