I reckon that either platform could give sufficient performance. Another question to ask is which platform your technical contributors are going to be most comfortable with. From what I have seen, developers are far more likely to be comfortable with a traditional relational database like postgres. Even at the systems level, you might have better luck sourcing a DBA to figure out scaling / performance issues than an LDAP guru.
That said, in my experience, the OpenLDAP has fewer "moving parts" and if your data can live in memory then there is very little tuning to do. LDAP is also handier to query from command-line, FWIW, and you could use it as an authentication mechanism for the contacts in your database if you wanted to do such a thing.
-danny