Try the following:
cv::Mat image = ...do some stuff...;
image.at<cv::Vec3b>(y,x);
gives you the RGB (it might be ordered as BGR) vector of type cv::Vec3b
image.at<cv::Vec3b>(y,x)[0] = newval[0];
image.at<cv::Vec3b>(y,x)[1] = newval[1];
image.at<cv::Vec3b>(y,x)[2] = newval[2];