Deprecated method in iOS 5:
// Override to allow orientations other than the default portrait orientation.
- (BOOL)shouldAutorotateToInterfaceOrientation:(UIInterfaceOrientation)interfaceOrientation 
{
    // Return YES for supported orientations
    return (interfaceOrientation == UIInterfaceOrientationLandscapeRight);
}
Replacement in iOS 6 and equivalent of this deprecated iOS 5 method above:
- (BOOL) shouldAutorotate
{
    return YES;
}
-(NSUInteger)supportedInterfaceOrientations
{
    return UIInterfaceOrientationMaskLandscapeRight;
}
Hope this helps.
[edit #1: Added my UIViewController which successfully starts in Portrait mode in XCode 4.5 on iPhone 6.0 Simulator]
#import "FirstViewController.h"
@interface FirstViewController ()
@end
@implementation FirstViewController
- (id)initWithNibName:(NSString *)nibNameOrNil bundle:(NSBundle *)nibBundleOrNil
{
    self = [super initWithNibName:nibNameOrNil bundle:nibBundleOrNil];
    if (self)
    {
        // Custom initialization
    }
    return self;
}
- (void)viewDidLoad
{
    [super viewDidLoad];
}
- (void)didReceiveMemoryWarning
{
    [super didReceiveMemoryWarning];
}
-(BOOL)shouldAutorotate
{
    return NO;
}
-(NSUInteger)supportedInterfaceOrientations
{
    return UIInterfaceOrientationMaskAll;
}
- (UIInterfaceOrientation)preferredInterfaceOrientationForPresentation
{
    return UIInterfaceOrientationMaskPortrait;
}
[#edit 2: Sample code from landscape only application which supports iOS 5 and iOS 6]
- (BOOL)shouldAutorotateToInterfaceOrientation:(UIInterfaceOrientation)interfaceOrientation {
    return (interfaceOrientation == UIInterfaceOrientationLandscapeRight) || (interfaceOrientation == UIInterfaceOrientationLandscapeLeft);
}
- (BOOL)shouldAutorotate {
    return YES;
}
- (NSUInteger)supportedInterfaceOrientations {
    return UIInterfaceOrientationMaskLandscape;
}
- (UIInterfaceOrientation)preferredInterfaceOrientationForPresentation {
    return UIInterfaceOrientationLandscapeLeft;
}