You are very close.
You applied the round to the series of values given by df.value1.
The return type is thus a Series.
You need to assign that series back to the dataframe (or another dataframe with the same Index).
Also, there is a pandas.Series.round method which is basically a short hand for pandas.Series.apply(np.round).
>>> df.value1 = df.value1.round()
>>> print df
item value1 value2
0 a 1 1.3
1 a 2 2.5
2 a 0 0.0
3 b 3 -1.0
4 b 5 -1.0