You will not get any kind of Compile error due to not having changed XML files, the compiler is totaly un-aware of the XML files. Once you have the new dll succesfully compiled though you will need to change XML files to get things working, if you remembered to initialize your variables properly and dont update the XML then you should just get no effect as all the variables remain NULL or zero when thouse new XML tags arn't found. Once your new XML files are are combined with the DLL you will get your data loaded into the game. Ofcorse you might get XML schema or loading errors if you didn't do them correctly (they are very picky). I recomend loading the new XML under un-moded dll this way you can check the loading and be shure that any problems are XML related and not with your new dll. Then combine XML and dll and pray it works, if it dosn't they you have a problem in the pStream->(XMLLodader) functions.
I speak from experience as this is currently the state of my Mod, which atempts to add a rather complex Matrix of SpecialistYield Changes to Technologies. These are much harder to do then single boolean or int values because of the numerous for loops to load the values. I recomend you be proficient with the simpler type before going for arrays or matrics.