1. How do I introduce the new external HDD2 into Lightroom without messing with the order?
You can simply connect the new external HDD and while importing the images into Lightroom just need to change the image destination to the new external HDD also, you can create the folder structure as per your requirement.
2. Do I create a new Catalogue2 for my new external HDD2 just to keep stuff separate?
Yes, it's better to create the new catalog with the new external HDD because you already have some many images imported into the existing catalog and it will also simplify the process to finding images in Lightroom catalog also, the performance will be better.
3. If I create a new Catalogue2 for the new HDD2, is it better to move the existing Catalogue1 (one I used with my first external hard drive) from my computer to the HDD1?
Well, if you don't have any use of that catalog for now and If it's taking too much space on your internal drive then, yes you can move the catalog on the existing external HDD and you can access the Lightroom catalog straight from the HDD as well, you don't have to move back to the internal HDD.
4. Is it possible to rename the Catalogue1 for it to match the HDD1 name for the ease of identification? If yes, how can I do it?
It's better if you rename catalog something specific for your identification so that you can make out which catalog is what.
Let me know if that helps.
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There is no need for a second catalog. A single catalog can manage images across multiple hard drives. I have images on three different hard drives myself. All you have to do is attach the new external hard drive and start importing images, setting the new hard drive as the destination drive. Lightroom will manage everything for you.