Попробуйте использовать set_index()
вот так:
new_df = df.set_index(['dt', 'st'])
Результат:
>>> new_df
close volume
dt st
20100101 000001.sz 1 10000
000002.sz 10 50000
000003.sz 5 1000
000004.sz 15 7000
000005.sz 100 100000
20100102 000001.sz 2 20000
000002.sz 20 60000
000003.sz 6 2000
000004.sz 20 8000
000005.sz 110 110000
>>> new_df.index
MultiIndex(levels=[[20100101, 20100102], ['000001.sz', '000002.sz', '000003.sz', '000004.sz', '000005.sz']],
labels=[[0, 0, 0, 0, 0, 1, 1, 1, 1, 1], [0, 1, 2, 3, 4, 0, 1, 2, 3, 4]],
names=['dt', 'st'])