"As" cast
(_pages[(int)ePage.Setup] as usSetup).SetupMethod();
If _pages[(int)ePage.Setup] is not usSetup, you will get NullReferenceException here, because (_pages[(int)ePage.Setup] as usSetup) will return null.
Direct cast
((ucSetup)_pages[(int)ePage.Setup]).SetupMethod();
If _pages[(int)ePage.Setup] is not usSetup, you will get InvalidCastException here.
Other than that, no differences.
By the way, I encourage you to follow .NET naming guidelines. Your classes should be named UCSetup (or UcSetup) and UCAddMorePagesHere (or UcAddMorePagesHere).
Alternative
You can simplify your code if you do the following:
public abstract class SetupPage : UserControl
{
    public abstract void SetupMethod();
}  
public class UcSetup : SetupPage
{
    public override void SetupMethod()
    {
        // Do something here
    }
}
public class UcAddMorePagesHere : SetupPage
{
    public override void SetupMethod()
    {
         // Do something here
    }
}
Then, instead of keeping list of UserControl's, keep list of SetupPage's
var _pages = new List<SetupPage>();
You will be able to call your method without a cast:
_pages[(int)ePage.Setup].SetupMethod();