Hi,
1. Well, if the system says that the alias of the product you're trying to create already exists, then it means that another entry in the hikashop_product table already exists with the same product_alias that you've provided in the "alias" field of the product you're trying to create. So if you look in the database, you should be able to find it. And that should lead to an explanation on why you can't find it.
For example, maybe it has a special product_type which isn't taken into account on the backend products listing ?
2. You could add these PDF files in the "Files" section of the "Images & Files& area of the product edit form. Once added, you'll want to edit the files to make sure that the "free download" checkbox is checked in the file edit popup. That way, the files will be available automatically on the product page.