Since you want every 3rd letter and not just the 3rd letter, we need to iterate the letters and generate the result according to the position of the character:
def cap_3rd(word):
result = ""
for i in range(1, len(word) + 1):
if i % 3 == 0:
result += word[i-1].upper()
else:
result += word[i-1]
return result
word = "thisisaverylonglongword"
print(cap_3rd(word)) # thIsiSavEryLonGloNgwOrd