In general, uncompressed image data is either 24bpp (RGB) or 32bpp (RGBA) flatrate. PVRTC is 4bpp (or 2bpp) flatrate so there is a compression of 6 or 8 (12 or 16) times compared to this.
A requirement for graphics hardware to use textures natively is that the format of the texture must be random accessible for the hardware. PVRTC is this kind of format, PNG is not and this is why PNG can achieve greater compression ratios. PVRTC is a runtime, deployment format; PNG is a storage format.
PVRTC compression is carried out on 4x4 blocks of pixels at a time and at a flat bit rate so it is easy to calculate where in memory to retrieve the data required to derive a particular texel's value from and there is only one access to memory required. There is dedicated circuitry in the graphics core which will decode this 4x4 block and give the texel value to your shader/texture combiner etc.
PNG compression does not work at a flat bitrate and is more complicated to retrieve specific values from; memory needs to be accessed from multiple locations in order to retrieve a single colour value and far more memory and processing would be required every single time a texture read occurs. So it's not suitable for use as a native texture format and this is why your textures must be decompressed before the graphics hardware will use them. This increases bandwidth use when compared to PVRTC, which requires no decompression for use.
So for offline storage (the size of your application on disk), PNG is smaller than PVRTC which is smaller than completely uncompressed. For runtime memory footprint and performance, PVRTC is smaller and faster than PNG which, because it must be decompressed, is just as large and slow as uncompressed textures. You might gain some advantage with PNG at initialisation for disk access, but then you'd lose time for decompression.
If you want to reduce the storage footprint of PVRTC you could try zip-style compression on the texture files and expand these when you load from disk.