No JavaScript necessary...
Option A
Give each list item a class, the same way you did the headers.
Option B
Use the +
(adjacent sibling) selector. Like this:
.top-tabs .tab:first-child,.head1 .region-header {
background-color: #014fa2;
}
.top-tabs .tab:first-child + .tab,.head2 .region-header {
background-color: #1e69b9;
}
.top-tabs .tab:first-child + .tab + .tab,.head3 .region-header {
background-color: #3481d2;
}
.top-tabs .tab:first-child + .tab + .tab + .tab,.head4 .region-header {
background-color: #58a1f0;
}
Try it out: http://jsfiddle.net/3q9cD/