Keys in web.config are not populated dynamically. I.E., you can't set a "macro" in web.config that pulls values from machine.config. But you shouldn't have too...
In your C# or VB.NET code, you pull values from machine.config exactly the same way you pull from web.config. ASP.NET knows to check in machine.config as well as web.config; and there are rules for which value overrides.
So, in your code, just stitch together your "ServerFileNames" path by making an appsettings lookup for "MachineName", and concatenating your "ServerFileNames" folder path.
Machine.config:
<add key="MachineName" value="ISCO1FEGRD"
Web.config:
<add key="ServerFileNames" value="\Dotnet_files\OrclIntlList.xml" />