So, first off you would
1. Add the new field into the main table (setting the correct datatype as well).
2. Then you would import the spreadsheet and tell it to use a NEW TABLE.
3. Then you would use an Update Query to update the existing records in the field in the main table by using an Update query like this (changing the names to your actual names)
Code:
UPDATE MainTableNameHere
INNER JOIN ImportedTableNameHere
ON MainTableNameHere.IDFieldNameHere=ImportedTableNameHere.IDFieldNameHere
SET MainTableNameHere.FieldToUpdateNameHere= [ImportedTableNameHere].[FieldWithNewDataHere]
WHERE (((ImportedTableNameHere.IDFieldNameHere)=[MainTableNameHere].[IDFieldNameHere]));