You should call SynchronizeRGBA(false) to copy from alpha plane to the A channel of the RGBA pixel.
Executing following code:
ImageEnView1->LegacyBitmap = false;
ImageEnView1->IO->LoadFromFile("test.png");
ImageEnView1->IEBitmap->PixelFormat = ie32RGB;
ImageEnView1->IEBitmap->SynchronizeRGBA(false);
ShowMessage(IntToStr(ImageEnView1->IEBitmap->Pixels_ie32RGB[0, 0].A));
"test.png" has the top-left pixel fully transparent (0), so this code shows correctly "0". Removing SynchronizeRGBA, shows "255" (not synched).