Laura --
Here's a recent thread from the Arkansas board about reasons why Confederates switched sides during the war. Most reasons for such a switch are thoroughly discussed.
http://history-sites.com/mb/cw/arcwmb/index.cgi?noframes;read=13469
In 1860 almost no white Southerner would have supported Abraham Lincoln and the Republican Party platform. At the same time, a substantial minority were strongly against secession. They are very different positions, which most people today would be unable to comprehend.
Once Lincoln called for troops, many former Southern Unionists volunteered for Confederate service. Thousands of those who fought to the bitter end had supported either the National Democratic (Douglas/Johnson) or the Constitutional Union Party (Bell/Everett) in the election of 1860.
http://members.aol.com/jfepperson/union.html
When someone says they were a unionist in politics that doesn't necessarily mean what we might think today.