The discovery of two-dimensional electron gases (2DEGs) at oxide interfaces-involving electrons in narrow d-bands-has broken new ground, enabling the access to correlated states that are unreachable in conventional semiconductors based on s- and p- electrons. There is a growing consensus that emerging properties at these novel quantum wells-such as 2D superconductivity and magnetism-are intimately connected to specific orbital symmetries in the 2DEG sub-band structure. Here we show that crystal orientation allows selective orbital occupancy, disclosing unprecedented ways to tailor the 2DEG properties. By carrying out electrostatic gating experiments in LaAlO3/SrTiO3 wells of different crystal orientations, we show that the spatial extension and anisotropy of the 2D superconductivity and the Rashba spin-orbit field can be largely modulated by controlling the 2DEG sub-band filling. Such an orientational tuning expands the possibilities for electronic engineering of 2DEGs at LaAlO3/SrTiO3 interfaces.