X-Ray basically is an extra file that needs to be downloaded to the device. It is downloaded once you purchase a book through Amazon - and it is available only on some books (the Amazon page clearly indicates which).
At times, you can find the same ebook in different editions in Amazon - some with X-Ray and some without. For example, I downloaded a copy of Pride and Prejudice without x-ray a while ago - when I realized I went to look for one with x-ray.
So, the short answer is no - you can't have x-ray for non-amazon content.
But... there is a but... you can actually 'fool' your kindle to download an x-ray file. Now, I don't know much about it... there was a thread on these forums a while ago. It basically comes down to changing some 'book identifier' on the kindle - so it thinks you have the Amazon version. I have not tried it, but I have seen threads about it.
Also, I have seen threads here about creating your own x-ray content. Again, I did not look into it.
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