Hey Andrew

Try below code and check what result you are getting.

function checkTitle() {
	var grUSER = new GlideRecord('sys_user');
	var grTITLE = new GlideRecord('u_title_list');
	grTITLE.query();
	
	while(grTITLE.next()){
		// grUSER.initialize();
		grUSER.addQuery('title', grTITLE.u_title);
		grUSER.query();
		
		if(!grUSER.next()){
			gs.print("IN if condition");// you were priting title from user table. If no record found then how system will print.
		}
		else
			gs.print("###HC :  In else condition."); // if this is print
	}
}