I agree, it shouldn't be that difficult. Part of the problem may be that I still don't entirely understand what you want to do.
What I was envisioning was:
The series representing the 2nd column is formatted a line w/o markers and the 3rd column is formatted as markers w/o a line. This "highlights" those two data points.
I didn't previously understand that the points you wanted to highlight would be between the existing data points. How best to approach this will depend on whether you are using a line chart or a scatter plot. Personally, I would use a scatter plot. Start with your original data set plotted. Then, somewhere in the spreadsheet add
Then paste this series into the scatter plot (use paste special so you can make sure Excel uses the 1st column as the x-values for this series). Or use the Chart->Source Data dialog to add the series. As before, the 1st series is formatted w/o markers and the 2nd series is formatted w/o lines.
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