Step 1: Select the first two columns of your block and generate a scatter plot. 1st column comes up as the X axis, 2nd column is the Y axis and the labels are correct.
Step 2: Select the third column and do a CTRL-C copy. Go to the graph and CTRL-V paste. Now the second series is plotted as it should be against the first column.
Repeat.
Sources:
The bottom of this thread gave me the clue that you can cut and past directly into a plot:
http://superuser.com/questions/770150/plot-multiple-sets-of-x-y-data-on-a-single-chart
Here's some entertaining rage, although it seems that the main problem was that the OP was confusing line charts with scatter plots:
http://answers.microsoft.com/en-us/office/forum/office_2010-excel/excel-chart-has-no-means-to-setchange-x-axis-data/fe76a57e-cc29-4cf1-bdf3-14857d9e682e?auth=1
Some more rage and a hint on doing manual edits to charts:
http://www.mrexcel.com/forum/excel-questions/512558-create-line-chart-first-column-x-axis.html