How to get hex color value rather than RGB value?

Here is the cleaner solution I wrote based on @Matt suggestion:

function rgb2hex(rgb) {
    rgb = rgb.match(/^rgb\((\d+),\s*(\d+),\s*(\d+)\)$/);
    function hex(x) {
        return ("0" + parseInt(x).toString(16)).slice(-2);
    }
    return "#" + hex(rgb[1]) + hex(rgb[2]) + hex(rgb[3]);
}

Some browsers already returns colors as hexadecimal (as of Internet Explorer 8 and below). If you need to deal with those cases, just append a condition inside the function, like @gfrobenius suggested:

function rgb2hex(rgb) {
    if (/^#[0-9A-F]{6}$/i.test(rgb)) return rgb;

    rgb = rgb.match(/^rgb\((\d+),\s*(\d+),\s*(\d+)\)$/);
    function hex(x) {
        return ("0" + parseInt(x).toString(16)).slice(-2);
    }
    return "#" + hex(rgb[1]) + hex(rgb[2]) + hex(rgb[3]);
}

If you're using jQuery and want a more complete approach, you can use CSS Hooks available since jQuery 1.4.3, as I showed when answering this question: Can I force jQuery.css("backgroundColor") returns on hexadecimal format?

var hexDigits = new Array
        ("0","1","2","3","4","5","6","7","8","9","a","b","c","d","e","f"); 

//Function to convert rgb color to hex format
function rgb2hex(rgb) {
 rgb = rgb.match(/^rgb\((\d+),\s*(\d+),\s*(\d+)\)$/);
 return "#" + hex(rgb[1]) + hex(rgb[2]) + hex(rgb[3]);
}

function hex(x) {
  return isNaN(x) ? "00" : hexDigits[(x - x % 16) / 16] + hexDigits[x % 16];
 }

(Source)

Most browsers seem to return the RGB value when using:

$('#selector').css('backgroundColor');

Only I.E (only 6 tested so far) returns the Hex value.

To avoid error messages in I.E, you could wrap the function in an if statement:

function rgb2hex(rgb) {
     if (  rgb.search("rgb") == -1 ) {
          return rgb;
     } else {
          rgb = rgb.match(/^rgba?\((\d+),\s*(\d+),\s*(\d+)(?:,\s*(\d+))?\)$/);
          function hex(x) {
               return ("0" + parseInt(x).toString(16)).slice(-2);
          }
          return "#" + hex(rgb[1]) + hex(rgb[2]) + hex(rgb[3]); 
     }
}