He studied law under John Tayloe Lomax and graduated from the University of Virginia in Charlottesville before marrying his cousin Frances Cornelia Baldwin in 1833.

Re-elected twice as a Whig to what were then single-year terms (and a position which is still part-time), Stuart served on the Committee for Courts of Justice and also advocated internal improvements (the James River Canal as well as railroads).

Although recommendations in his critical report concerning deficiencies in such improvements were not adopted, during 1838 Stuart became a junior member of the Committee on Roads and Internal Navigation.

[1] In 1840 Stuart won election as a Whig to the 27th Congress, as the incumbent Jacksonian Democrat Robert Craig declined to run for re-election.

Wise criticized the Know Nothings, Stuart (as "Madison") published twelve long letters on the "American Question" in the Richmond Whig and Public Advertiser and later as a combined pamphlet.

He was the senior senator on the committee to investigate John Brown's Raid against the arsenal in Harper's Ferry (then still in Virginia) in October 1859.

The committee's report condemned abolitionist agitation, and recommended strengthening local militia units, as well as achieving commercial independence from the North by encouraging Virginia's domestic manufactures.

In the 1860 U.S. Presidential Election, Stuart supported the Constitutional Union Party and its candidate, John Bell (a former Whig who had represented Tennessee in the U.S. Congress).

Augusta County voter elected Unionists Stuart, John Brown Baldwin (his brother-in-law) and George Baylor to represent them in the Virginia Secession Convention of 1861.

Stuart, William B. Preston and George W. Randolph as a special Virginia delegation traveled to Washington, D.C., and met President Lincoln on April 12 after the surrender of Fort Sumter.

Finding Lincoln firm in his resolve to hold the federal forts in the South, the three men returned to Richmond, Virginia on April 15.

[1] About a month after Virginia's surrender at Appomattox Courthouse, on May 8, 1865, Stuart chaired a mass meeting in Staunton, which adopted resolutions asking the U.S. Army's protection and declaring the populace not in rebellion.

However, despite presenting credentials as a member-elect to the 39th Congress in 1865, he was denied a seat as were other newly-elected Southern delegates, because Virginia was not yet readmitted to the Union, pending its adoption of a new state constitution outlawing slavery, among other measures.

Shortly after it convened, Stuart became chairman of the Committee of Nine, which lobbied the new president Ulysses S. Grant, and managed to secure separate votes for the new state constitution, which passed overwhelmingly, and anti-Confederate measures, which failed.

He also served as president of the Virginia Historical Society from 1881 to his death, published a booklet concerning the Committee of Nine at its request, and continued his legal practice.