They can both be an excellent material, but it depends on what the criteria for comparison are. If you want density and stiffness, MDF is better. If you want light and stiff, plywood is the better choice. Both are available in versions that have decreased off-gassing, so chemical sensitivity won't be as much of an issue. Both are dimensionally stable as long as all surfaces/edges are sealed to prevent moisture absorption. Avoiding inhalation of the dust is recommended for all wood products, especially if they have chemicals in them. It's best to use mechanical fasteners with both because when a speaker enclosure is being designed, it's the air vibrations that are creating the sound and anything that comes from the cabinet resonances will affect the end result. Ideally, you want the cabinet to be totally inert and one layer of either will miss on this issue. Internal bracing helps to place the resonance frequencies outside of the range of the driver's use. The more energy a driver imparts on the enclosure, the more mass and stiffness are required. IMO, extremely light and stiff isn't going to be the best because the cone's motion will try to move the assembly (that pesky Law of Physics about action applied resulting in an equal and opposite reaction). If the woofer cone assembly pushes in one direction, the rest of it has to push back in the opposite direction if it's going to remain motionless.