For mixed position and index, use .ix. BUT you need to make sure that your index is not of integer, otherwise it will cause confusions.
df.ix[0, 'COL_NAME'] = x
Update:
Alternatively, try
df.iloc[0, df.columns.get_loc('COL_NAME')] = x
Example:
import pandas as pd
import numpy as np
# your data
# ========================
np.random.seed(0)
df = pd.DataFrame(np.random.randn(10, 2), columns=['col1', 'col2'], index=np.random.randint(1,100,10)).sort_index()
print(df)
      col1    col2
10  1.7641  0.4002
24  0.1440  1.4543
29  0.3131 -0.8541
32  0.9501 -0.1514
33  1.8676 -0.9773
36  0.7610  0.1217
56  1.4941 -0.2052
58  0.9787  2.2409
75 -0.1032  0.4106
76  0.4439  0.3337
# .iloc with get_loc
# ===================================
df.iloc[0, df.columns.get_loc('col2')] = 100
df
      col1      col2
10  1.7641  100.0000
24  0.1440    1.4543
29  0.3131   -0.8541
32  0.9501   -0.1514
33  1.8676   -0.9773
36  0.7610    0.1217
56  1.4941   -0.2052
58  0.9787    2.2409
75 -0.1032    0.4106
76  0.4439    0.3337