There is one difference between the first two URL's - the first one has "And" in the URL while the second one has "and". This will matter if (as is commonly the case) the file names are case significant on the web server.
I have found this can happen if using Calibre on Windows and when updating the metadata the title or author are updated with the only difference being case. Since Windows file systems are case insignificant the file rename is effectively ignored by Windows and you end up with the filename and the calibre metadata disagreeing on the case. The Calibre2Web script always uses the case from the Metadata when generating the catalog files.
As this problem does not occur when creating new files, the workaround is to edit the title (or author if that is where the discrepancy occurs) to some other value (I normally just add an "X" on the end) and then after committing that change changing it back. This will make the metadata and filenames agree on case.
The point you mention about spaces (or other special characters) should not matter as they should always be escaped using %xx syntax as shown in your examples.
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