One of these is possibly his first marriage:

Surname First name(s) District Vol Page
Marriages Sep 1853   (>99%)
BAINES Matthew Chelsea 1a 260   
BARNES Laura Susanna Chelsea 1a 260   
Bryant Edmund Howard Chelsea 1a 260   
Diggens Jane Chelsea 1a 260

In the 1861 census these Edmund Bryants with Laura or Jane wives were to be found:
(a) aged, 32, wife is Jane with a dau age 6 and son aged 5m in St Giles, London.
(b) aged 44, wife is Jane, eldest s. is 14, living in Battle Sussex (NO)
(c) aged 32, wife is Jane, eldest s. is 8, living in Bedfordshire (POSS)

This means that it is very possible that Matthew Baines’ first wife was Laura Susanna Barnes.
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In 1861 he was a widower with his daughter Laura May, who stayed at home until he died in 1906:

Name Relation Condition Sex Age Birth Year Occupation  Disability  Where Born

BAINES, Mathew Head Widower M 37 1824 Md University Of London General Practioner
St Marylebone London, Middlesex
BAINES, Laura May Daughter Child F 7 1854   St Marys Abbotts Kensington, Middlesex
BEACH, Susan Servant Unmarried F 34 1827 Nurse  London, Middlesex
WARDER, Ann Servant Unmarried F 34 1827 Cook  London, Middlesex
THORP, William Servant Unmarried M 15 1846 Page  London, Middlesex

RG number: RG09 Piece: 21 Folio: 39 Page: 21    

Registration District: Kensington Sub District: 4 Brompton EnumerationDistrict: 6
Ecclesiastical Parish: Holy Trinity

Civil Parish: Kensington Municipal Borough:
Address: 54, Thurloe Square, Kensington
County: London, Middlesex
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In the 1881 census he was a doctor in 11 Cranley Place, Mx and aged 56.

Name Relation Condition Sex Age Birth Year Occupation  Disability  Where Born

BAINES, Mathew Head Married M 56 1825 Physician M. D. London  London, London, Middlesex
BAINES, Elizabeth Wife Married F 47 1834   Medmenham, Buckinghamshire
BAINES, Louise Mary Daughter Single F 26 1855   London, London, Middlesex
BAINES, Matilda Wordly Daughter Single F 10 1871 Scholar  London, London, Middlesex
CHIVERS, Elizabeth Servant Single F 37 1844 Nurse  St Johns, Lincolnshire
WRIGHT, Elizabeth Servant Single F 34 1847 Cook  Cottenham, Cambridgeshire
BASEL, Maria Servant Single F 22 1859 Parlour Maid  St Marys, Norwich, Norfolk
ROBE, Emma Servant Single F 19 1862 Housemaid  Egham, Surrey

RG number: RG11 Piece: 45 Folio: 39 Page: 15    

Registration District: Kensington Sub District: Brompton EnumerationDistrict:
Ecclesiastical Parish:

Civil Parish: Kensington Municipal Borough:
Address: 11, Cranley Place, Kensington
County: Middlesex

The above gave his year of birth from which I could pick the right death of the 20 Matthew Baines on FreeBMD.
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In 1891 they were:

Name Relation Condition Sex Age Birth Year Occupation  Disability  Where Born

BAINES, Mathew Head Married M 67 1824 Registered Medical Practitioner  St Marylebone, London
BAINES, Elizabeth Wife Married F 57 1834   Midmenham, Buckinghamshire
BAINES, Laura M Daughter Single F 36 1855   Brompton, London
BAINES, Arthur W P Son Single M 27 1864 Clerk  Brompton, London
BURNE, Ann Servant Widow F 51 1840 Domestic Servant  Witchelsea, Cambridgeshire
FLEET, Annie E J Servant Single F 24 1867 Domestic Servant  North Crawley, Buckinghamshire
SMITH, Alice M Servant Single F 28 1863 Domestic Servant  London

RG number: RG12 Piece: 30 Folio: 175 Page: 19

Registration District: Kensington Sub District: Brompton EnumerationDistrict: 8
Ecclesiastical Parish: St Paul

Civil Parish: Kensington Municipal Borough:
Address: 11, Cranley Place, Kensington
County: London
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In the 1901 census, they were down as Barnes:

Sched Name Relation Condition Sex Age Birth Year  Occupation,  Disability  Where Born

   120 BARNES, Matthew Head Married M 77 1824 Physician  S Kensington, London
   120 BARNES, Elizabeth Wife Married F 68 1833   Medmenham, Buckinghamshire
   120 BARNES, Laura M Daughter Single F 46 1855  S Kensington, London
   120 BARNES, Hilda W P Daughter Single F 30 1871  S Kensington, London
   120 JEFFREYS, Mary A Servant Widow F 68 1833   Cook Domestic   Diss, Norfolk
   120 WEBSTER, Louisa J Servant Widow F 21 1880  Parlour Maid Domestic  S Kensington, London
   120 COLLARD, Martha Servant Single F 19 1882   House Maid Domestic  S Kensington, London

RG number: RG13 Piece: 35 Folio: 91 Page: 22    

Registration District: Kensington Sub District: Brompton Enumeration District: 10
Ecclesiastical Parish: St Pauls Onslow Square

Civil Parish: Kensington Municipal Borough:
Address: 11, Cranley Place, Kensington
County: London

Hilda is the daughter who was shown as Matilda Worsley in the 1881 census and was registered in Q4 of 1870 as Hilda Worsley P.
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It is almost certain that all his and Elizabeth’s children d.unm. and sp.