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Thanks to kcrisman I figured the remaining bits out myself. Complete code as follows:

# [...]
print latex(sexp)
sexp2=simplify(sexp) # expand doesn't hurt it, so omit that
print latex(sexp2)
# observe they are different due to sexp2 being processed 
# via Maxima, as explained by kcrisman
# maxima replaces a() by a new a() that doesn't have the 
# print function:

print sexp2.operands()[0].operator().__class__ # maxima a()
print a.__class__ # the a() we have defined

# to coerce back, we need to replace the former by the latter:
print latex(sexp2.substitute_function(sexp2.operands()[0].operator(),a))

Thanks to kcrisman I figured the remaining bits out myself. Complete code as follows:

# [...]
print latex(sexp)
sexp2=simplify(sexp) # expand doesn't hurt it, so omit that
print latex(sexp2)
# observe they are different due to sexp2 being processed 
# via Maxima, as explained by kcrisman
# maxima replaces a() by a new a() that doesn't have the 
# print function:

print sexp2.operands()[0].operator().__class__ # maxima a()
print a.__class__ # the a() we have defined

# to coerce back, we need to replace the former by the latter:
print latex(sexp2.substitute_function(sexp2.operands()[0].operator(),a))

(And that does the intended.)