... and two suggestions to the development team

POINT 1
In ?DiscreteValueMap (package Statistics) it's given an example concerning rhe Geometric distribution along with this comment:
"The Geometric distribution is discrete but it necessarily assumes integer values, so (bold font is mine) it also does not have a DiscreteValueMap"

This sentence seems to indicate that "because a distribution is discrete over the set of integers, it cannot have a DiscreteValueMap", some sort of logical implication...

But my feeling is that the Geometric distribution (or any other discrete distribution) does not have a DiscreteValueMap because this attribute has just not been specified when defining the distribution.

restart:
with(Statistics):

GeomRV := RandomVariable(Geometric(1/2)):
f := unapply(ProbabilityFunction(GeomRV, n), n):

AnotherGeomRV := Distribution(
      'ProbabilityFunction'=f,
      'Support'=0..infinity,
      'DiscreteValueMap'=(n->n),
      'Type'=discrete
):
DiscreteValueMap(AnotherGeomRV , n);

Thus having the set of natural numbers as support doesn't imply that DiscreteValueMap cannot exist.

Suggestion 1: modify the ?DiscreteValueMap help page so that it no longer suggests that some discrete distributions cannot have a .DiscreteValueMap 

______________________________________________________________________________________

POINT 2
I think there exists a true problem with the definition of discrete distributions in Maple: the ProbabilityFunction of a (discrete) random variable) takes non zero values outside their definition set.
For instance

ProbabilityFunction(GeomRV, Pi);  # something non null

To ivercome this problem I defined a new Geometric distribution this way (not entirely satisfying):

restart:
with(Statistics):

GeomRV := RandomVariable(Geometric(1/2)):
f := unapply(ProbabilityFunction(GeomRV, n), n):
g := n -> (1-ceil(n-floor(n)))*f(n)    # (1-ceil(n-floor(n))) = 1 if n in Z, 0 otherwise

AnotherGeomRV := Distribution(
      'ProbabilityFunction'=g,
      'Support'=0..infinity,
      'DiscreteValueMap'=(n->n),  # is wanted
      'Type'=discrete
):
ProbabilityFunction(AnotherGeomRV, 2);
                 1/8
ProbabilityFunction(AnotherGeomRV, Pi);
                  0

PS: None of the statistics based upon the  ProbabilityFunction (Mean, Variance, ... ) is correctly computed with the previous construction. This could be easily overcome by completing this definition, just as its done in Maple, for all the requires statistics, for instance 

AnotherGeomRV := Distribution(
      ....
      'Mean'=1   # or more generally (1-p)/p form Geometric(p)
):

Suggestion 2: modify the way discrete distributions are defined in Maple in order to avoid ProbabilityFunction to return wrong values.