Yes, you can do that.
If you just want to add a new empty image (or copy one of the exiting ones) into an existing .ico file, click on Insert image... in the Icon menu and choose Custom format. There you can specify custom dimensions for you new image.
If you want to create icon from image (or 3D), you can add new formats to generate during in the conversion window. When you see the list of formats with previews, click on Add image and then double-click the image to display its properties and change them.