Alas, I was misinterpreting some of the functionality. Centering across all pages can be done like so:
myImage = section.Headers.EvenPage.AddImage("C:\\myImage.png");
myImage.Height = "4.5cm";
myImage.LockAspectRatio = true;
myImage.Top = MigraDoc.DocumentObjectModel.Shapes.ShapePosition.Center;
myImage.Left = MigraDoc.DocumentObjectModel.Shapes.ShapePosition.Center;
myImage.RelativeHorizontal = MigraDoc.DocumentObjectModel.Shapes.RelativeHorizontal.Margin;
myImage.RelativeVertical = MigraDoc.DocumentObjectModel.Shapes.RelativeVertical.Margin;