So this is how the problem was solved for anyone interested:
Declare your variables within the 'if' statement. If they are false, the output would result in one URL; if true, a different URL and different voting button image. (In this case, if the user was logged in or not.) The "alt" is for the Alternate Text you must provide for any image placement, so we'd want this different if the image was different, obviously.
<?php
ob_start();
session_start();
if(!isset($_SESSION['Username']))
{
$alt = 'Please Register';
$link = 'http://www.test.com/signup.php';
$img = '/images/register_but.png';
} else {
$alt = 'Vote!';
$link = 'http://www.test.com/thanks.php';
$img = '/images/vote_but.png';
}
?>
And the calls for the variables would look like this where your voting buttons would be (or variable URLS and respective images).
<a href="<?php echo $link; ?>"><img src="<?php echo $img; ?>" alt="<?php echo $alt; ?>" />
Thanks again to fobos and phorce for your help. I over thought this one as usual. Keep It Simple Stupid are words to code by.