Use Word 2010's Numbering feature in tables and make it automatically number multiple table columns vertically. This way, each cell in each column will be placed under the correct number.

Word will assign the same set of numbers to the second column. Right-click the number in the first row of the second column and choose Set Numbering Value.

You can use built-in options to build a simple table of contents, but quite often, you'll need to change the underlying field code to get the results you want.