Prior to the Civil War, Munford was a cotton planter in Mississippi and farmer in Bedford County, Virginia.

With the outbreak of the Civil War, Munford was mustered into the Confederate States Army on May 8, 1861 by Colonel Jubal A.

"Stonewall" Jackson as commander of a cavalry brigade of two regiments,[3] succeeded Colonel and acting Brigadier General Turner Ashby as commander of all of Jackson's cavalry, upon that officer's death, and fought well at the Battle of Cross Keys and captured many prisoners at Harrisonburg, Virginia.

[3] During that campaign he successfully cleared Leesburg, Virginia of Union forces at the Battle of Mile Hill so that the army could cross the Potomac River from there.

He led his troops in a key defensive position protecting Crampton's Gap at the Battle of South Mountain.

[1] He led men away from the Army of Northern Virginia prior to General Robert E. Lee's surrender at Appomattox Court House and escaped with a goal of reaching North Carolina to link up with the army of General Joseph E. Johnston during the Carolinas Campaign.