A solution without accessing the DataFrame is to use the patches attribute:
ax = df.plot.bar(title="Scores")
for p in ax.patches:
ax.annotate(str(p.get_height()), xy=(p.get_x(), p.get_height()))
Note you have to play around with the xy kwarg (2nd arg) to get the label position you desire.
Vertical Bars
I found this formatting to be the best in general:
ax.annotate("%.2f" % p.get_height(), (p.get_x() + p.get_width() / 2., p.get_height()), ha="center", va="center", xytext=(0, 10), textcoords="offset points")
Horizontal Bars
I found the following format to work well with horizontal bars:
ax.annotate("%.2f" % p.get_width(), (p.get_x() + p.get_width(), p.get_y()), xytext=(5, 10), textcoords="offset points")