After attending private schools around Winchester, young Baldwin traveled to Williamsburg to study at the College of William and Mary, from which he graduated in 1807.

The Baldwins lived at "Spring Hill Farm", a house built by Hessian prisoners during the American Revolutionary War.

Augusta County voters elected him to represent them in the Virginia House of Delegates four times, beginning in December 1818, when he and Andrew Anderson replaced the incumbents and were both re-elected in 1819, but neither won in 1820.

Baldwin again won election in 1841, but failed to complete his term, resigning after fellow legislators appointed him to a vacant seat on the Virginia Court of Appeals.

His son John Brown Baldwin would follow his father's legal, military and legislative path, including partnership with Alexander H.H.

Although he opposed secession, J.B. Baldwin briefly served as colonel of the 52nd Virginia Infantry during the conflict, resigning his commission in order to represent Staunton and the surrounding region in the Confederate States Congress, during which he became one of President Jefferson Davis' most vocal critics.

A large collection consisting almost solely of the legal, financial, and personal correspondence of Archibald Stuart and Briscoe Baldwin, lawyers from Staunton, and their related family letters is housed at the University of Virginia.