for num in list(dataframe.['CLI_ID'].values):

   ...some code lines, to sum columns...
   print(values)

{"num_1":{"item1":4}}
{"num_2":{"item19":6,"item20":4,"item18":4}}
...
{"num_99":{"item18":5,"item21":4,"item20":1}}

with open('values.json', 'w') as outfile: json.dump(values, outfile)