Is it possible to arrange the order of movies in iTunes?
Unfortunately, I don't have enough videos to test this.

Using The Lord of the Rings: The Fellowship of the Ring for example:

Open the movie's Get Info:
Go to the Video tab and set, for example:


  Show: The Lord of the Rings
  Episode Number: 1


Go to the Sorting tab and set:


  Name: The Lord of the Rings: The Fellowship of the Ring
  Sort Name: Lord of the Rings