By default, groupby output has the grouping columns as indicies, not columns, which is why the merge is failing.
There are a couple different ways to handle it, probably the easiest is using the as_index parameter when you define the groupby object.
po_grouped_df = poagg_df.groupby(['EID','PCODE'], as_index=False)
Then, your merge should work as expected.
In [356]: pd.merge(acc_df, pol_df, on=['EID','PCODE'], how='inner',suffixes=('_Acc','_Po'))
Out[356]:
EID PCODE SC_Acc EE_Acc SI_Acc PVALUE_Acc EE_Po PVALUE_Po \
0 123 GR 236 40000 1.805222e+31 350 10000 50
1 123 GR 236 40000 1.805222e+31 350 30000 300
2 123 GU 443 12000 8.765549e+87 250 10000 100
3 123 GU 443 12000 8.765549e+87 250 2000 150
SC_Po SI_Po
0 23 40
1 213 140
2 230 400
3 213 140