попробуй:
import matplotlib.pyplot as plt
import pandas as pd
df = pd.DataFrame({'A':[1,2,3,1,2,3],'B':[1.3,2.6,3.2,5.6,4.5,3.1]})
fig, ax = plt.subplots()
ax.plot(df.A, df.B, '-')
temp = df.groupby('A')['B'].min().reset_index()
ax.plot(temp.A, temp.B, 'r-')