You can iterate through the rows in the list store ( for row in liststore:...), as well as through the columns (values) in each row ( for col_value in row:...).
For simple, direct updates:
row_n = 0
col_n = 2
liststore[row_n][col_n] = 'new value'
gtk.TreeIter (row_iter):
liststore.set_value(row_iter, col_n, 'new value')